bluuebunny/crossref_metadata_2025 huggingface dataset:
Ultrahigh Specific Strength by Bayesian Optimization of Carbon Nanolattices
Authors: Serles Peter , Yeo Jinwook , Haché Michel , Demingos Pedro Guerra , Kong Jonathan , Kiefer Pascal , Dhulipala Somayajulu , Kumral Boran , Jia Katherine , Yang Shuo , Feng Tianjie , Jia Charles , Ajayan Pulickel M. , Portela Carlos M. , Wegener Martin , Howe Jane , Singh Chandra Veer , Zou Yu , Ryu Seunghwa , Filleter Tobin
Published: January 2025

Nanoarchitected materials are at the frontier of metamaterial design and have set the benchmark for mechanical performance in several contemporary applications. However, traditional nanoarchitected designs with conventional topologies exhibit poor stress distributions and induce premature nodal failure. Here, using multi‐objective Bayesian optimization and two‐photon polymerization, optimized carbon nanolattices with an exceptional specific strength of 2.03 MPa m3 kg−1 at low densities <215 kg m−3 are created. Generative design optimization provides experimental improvements in strength and Young's modulus by as much as 118% and 68%, respectively, at equivalent densities with entirely different lattice failure responses. Additionally, the reduction of nanolattice strut diameters to 300 nm produces a unique high‐strength carbon with a pyrolysis‐induced atomic gradient of 94% sp2 aromatic carbon and low oxygen impurities. Using multi‐focus multi‐photon polymerization, a millimeter‐scalable metamaterial consisting of 18.75 million lattice cells with nanometer dimensions is demonstrated. Combining Bayesian optimized designs and nanoarchitected pyrolyzed carbon, the optimal nanostructures exhibit the strength of carbon steel at the density of Styrofoam offering unparalleled capabilities in light‐weighting, fuel reduction, and contemporary design applications.
Imidazolium‐Dithiocarboxylate Zwitterions Catalysed Ring‐Opening Additions of Cyclopropenones
Authors: Wu Qi , Zhang Fang , Zhang Qichao , He Lin , Liu Jichang , Du Guangfen
Published: January 2025

Imidazolium‐dithiocarboxylate zwitterions (NHC ⋅ CS2), a novel organocatalyst that derived from N‐heterocyclic carbene (NHC), was used to activate cyclopropenones. Under the catalysis of 10 mol% NHC ⋅ CS2, a range of phenols, alcohols, primary and secondary amines react with cyclopropenones to produce trisubstituted α, β‐unsaturated esters and amides in 46–95% yield. More than 68 products, including 7 natural product derivatives have been synthesized through this method. Mechanism study showed NHC ⋅ CS2 act as a Lewis base to activate the C=C double bond of cyclopropenones and trigger the ring‐opening reaction. HRMS analysis indicated the formation of the key adduct of NHC ⋅ CS2 and cyclopropenone. More importantly, this study demonstrated completely different catalytic activity of NHC ⋅ CS2 and NHC catalysts, the latter one cannot catalyse these reactions.
Bee Better: The Role of Honey in Modern Wound Care
Authors: Tricou Léo‐Paul , Guirguis Natalie , Djebbar Sarah , Freedman Benjamin R. , Matoori Simon
Published: January 2025

Honey has been used as an empirical wound care agent for thousands of years and continues to be investigated and used in chronic wound care. In the past few years, several commercially available medical grade honey‐based products have been approved for chronic wound therapy. Clinical trials showed that the therapeutic benefit of honey depends on wound type and honey composition. Recent insights into the pharmacology of honey in wound therapy over the past two decades have led to increased interest in this natural remedy and highlighted various antimicrobial and immunomodulatory properties that contribute to its pharmacologic action. However, the interaction between honey and the wound microenvironment on wound healing remains unclear. In this perspective, the current clinical evidence supporting the use of honey in wound care is presented and highlights its molecular mechanisms of action to eventually critically discuss the opportunities and challenges of using honey in wound care.
2‐oxo‐2H‐chromen‐7‐olate Catalyzed C−C and C−N Bond Formations in Visible Light
Authors: Dixit Vikas , Sharma Shruti , Jain Nidhi
Published: January 2025

7‐hydroxycoumarin is a naturally occurring compound with useful biological and fluorescent properties. In this work, we demonstrate a base‐assisted photoactivation of 7‐hydroxycoumarin in blue LED and its potential in enabling C−C and C−N bond formations. 7‐hydroxycoumarin, on deprotonation with Cs2CO3 forms 2‐oxo‐2H‐chromen‐7‐olate which exhibits photoreductant properties and mediates arylation and hydroxyarylation using hypervalent iodonium ylides; alkylation using N‐hydroxyphthalimide esters; and amination with primary and secondary amines. The strategy does not require any additional metal or organic dye‐based photocatalyst and offers a good functional group tolerance giving the C−C and C−N coupled products in moderate to good yields.
Nanoplasmonics for Enhanced Fluorescence Detection of Nucleic Acids: From Fundamentals to Boosting Cancer Management
Authors: Botequim David , Oliveira‐Silva Rui , Serra Vanda Vaz , Zijlstra Peter , Prazeres Duarte Miguel de França , Paulo Pedro Miguel Ribeiro
Published: January 2025

Cancer remains a leading cause of mortality and morbidity worldwide. Consequently, the scientific community continues to pursue improvements in diagnostic methods and subsequent treatments. To enhance treatment efficacy and reduce the probability of adverse outcomes, reliable and sensitive diagnostic methods are essential. A potential solution may lie in the synergy between nanotechnology and optical biosensors, as they can provide exceptional sensitivity in the detection of disease biomarkers. This review focuses on fluorescent DNA probes assembled onto metal nanoparticles for cancer‐related applications. These hybrid biosensors exhibit remarkable and versatile optical properties enabling to enhance signal emission by orders of magnitude. In these configurations, metallic particles function as optical antennas for fluorescent dyes, significantly increasing their photon emission rates. This review presents a novel perspective on recent advancements in cancer diagnostics and treatment utilizing hybrid biosensors. Current methodologies for cancer diagnostics are examined, toward elucidating their advantages and limitations. The subject matter is critically evaluated, and fundamental concepts are explored to assess the most promising avenues for clinical applications. These biosensors may potentially integrate into medical practice and healthcare in the near future, both for the diagnosis and prognosis of cancer, as well as for precision (P4) medicine.
Broad‐Temperature Optical Thermometry via Dual Sensitivity of Self‐Trapped Excitons Lifetime and Higher‐Order Phonon Anharmonicity in Lead‐Free Perovskites
Authors: Niu Guangming , Jiang Jutao , Zeng Xiangyu , Liu Xin , Wang Xiaowei , Zhang Yutong , Che Li , Sui Laizhi , Wu Guorong , Yuan Kaijun , Yang Xueming
Published: January 2025

Broad‐temperature optical thermometry necessitates materials with exceptional sensitivity and stability across varied thermal conditions, presenting challenges for conventional systems. Here, we report a lead‐free, vacancy‐ordered perovskite Cs2TeCl6, that achieves precise temperature sensing through a novel combination of self‐trapped excitons (STEs) photoluminescence (PL) lifetime modulation and unprecedented fifth‐order phonon anharmonicity. The STEs PL lifetime demonstrates a highly temperature‐sensitive response from 200 to 300 K, ideal for low‐to‐intermediate thermal sensing. In contrast, the Eg phonon mode undergoes significant linewidth broadening due to five‐phonon scattering processes, with a distinct nonlinear temperature dependence up to 500 K. This fifth‐order anharmonic effect enhances Raman‐based temperature sensitivity, yielding a specific sensitivity (Sr) of 0.577 % K–1 at 330 K and remaining above 0.5 % K–1 at elevated temperatures. This study presents the first evidence of fifth‐order anharmonic effects enhancing Raman‐based temperature sensitivity, establishing Cs2TeCl6 as a versatile candidate for broad‐temperature optical thermometry and opening new avenues for precise non‐contact temperature sensing in advanced technological applications.
Crystalline, Porous Figure‐Eight‐Noded Covalent Organic Frameworks
Authors: Li Yaling , Tao Shanshan , Chen Yongzhi , Ye Xingyao , Shao Haipei , Lin Ming , Zhi Yongfeng , Jiang Donglin
Published: January 2025

Figure‐eight macrocycles represent a fascinating class of π‐conjugated units characterized by unique aesthetics and non‐contact molecular crossing at the center. Despite progress in synthesis over the past century, research into inorganic, organic, and polymeric figure‐eight materials remains in its infancy. Here we report the first examples of figure‐eight covalent organic frameworks by condensing figure‐eight knots to create extended porous figure‐eight π architectures. A distinct feature is that polymerization interweaves figure‐eight knots into double‐decker layers, which upon supramolecular polymerization organize well‐defined layer frameworks. The figure‐eight frameworks exhibit a band gap of 2.3 eV and emit bright orange florescence with benchmark quantum yields. Remarkably, the donor‐acceptor figure‐eight skeletons convert the figure‐eight knots into reduction centers and the linkers into oxidation sites upon light irradiation, enable charge transport and accumulation through π columns, while the built‐in hydrophilic micropores allow rapid water and oxygen delivery via capillary effect. With these distinct features, the figure‐eight frameworks function as a photocatalyst to produce hydrogen peroxide at high rate and efficiency with water/saltwater, oxygen/air, and light as sole inputs. This work paves a way to a new class of molecular frameworks, underpinning the study of well‐defined figure‐eight materials to explore unprecedented structures and functions so far we untouched.
Dual‐Asymmetric Solid Additive Enables Eco‐friendly All‐Polymer Solar Cells with Over 19 % Efficiency and Excellent Stability
Authors: Liang Qiming , Li Henan , Xu Wan , Lu Junyi , Ma Ruijie , Bai Qingqing , Sun Xiaokang , Chen Mingqing , Zhu Liangxiang , Liu Qian , Guo Yuting , Zhang Guangye , Xue Qifan , Iwan Agnieszka , Cheng Pei , Hu Hanlin , Wang Hua , Chen Junwu , Niu Li , Sun Huiliang
Published: January 2025

The optimization of morphology in all‐polymer solar cells (all‐PSCs) often relies on the use of solvent additives. However, their tendency to remain trapped in the device due to high boiling points leads to performance degradation over time. In this study, we introduce a novel approach involving the design and synthesis of one dual‐asymmetric solid additive featuring mono‐brominated‐asymmetric dithienothiophene (SL‐1). Leveraging the synergistic effects of asymmetric substitution and core structures, fine‐tuning the molecule dipole moment enhancing solid additive interactions with host materials, thereby regulating polymer aggregation and influencing blend morphology during device fabrication. This results in highly ordered π–π stacking and a favorable phase‐separated morphology within all‐polymer active layer. Our work achieved a record efficiency of 19.19 % in eco‐friendly all‐PSCs, significantly outperforming SL‐0 (18.37 %) and SL‐2 (16.60 %), both featuring an asymmetric core. Furthermore, SL‐1‐treated all‐PSCs retain over 90 % of their initial efficiency after 2140 hours of operation, with an extrapolated T80 lifetime reaching 12400 hours. This represents a significant improvement in stability compared to devices treated with solvent additive (1‐CN), which typically exhibits a T90 lifetime of 700 hours. Our findings underscore the efficacy of utilizing dual‐asymmetric solid additives as a straightforward and viable strategy for optimizing all‐polymer morphology. SL‐1 represents a promising advancement towards eco‐friendly fabrication and application of high‐efficiency and stable all‐PSCs.
Applications of Verdazyl Radicals in Energy Storage, Molecular Electronics and Magnetism: Teaching Old Molecules New Tricks
Authors: Duggin Margot , Bissember Alex C. , Fuller Rebecca O.
Published: January 2025

Verdazyls are a fundamental class of stable organic radicals that have been traditionally overshadowed by the more synthetically accessible stable nitroxide radicals. With the advent of enhanced synthetic routes to verdazyls, particularly in recent years, these systems are now poised to realise their potential in a range of applications across emerging technologies that will be important to addressing challenges faced by modern society. This review discusses the enabling properties of a selection of verdazyl‐based systems that feature promising applications in energy storage, molecular electronics and magnetic molecules. Emphasis is placed on progress in these areas over the past ~5 years.
Waves of Change: African American Leaders Transforming the Water Sector
Authors: Parks Carita
Published: January 2025

Key Takeaways

AWWA members and water utility leaders are paving the way for expanded diversity—and a focus on welcoming and belonging—in the water industry as envisioned in AWWA's 2030 Strategic Plan and Water 2050 initiative.

With a growing number of African American water professionals setting the tone for the utilities they lead, their communities benefit from a heightened level of understanding.

Being an African American leader in the water industry has unique challenges, but setting an example for underrepresented professionals and future generations is an integral driver of their work.

The seven people interviewed for this article stressed common leadership principles: building relationships, aligning with customers’ needs; advocating for diversity, equity, inclusion, and belonging; removing barriers to professional growth; and inspiring newcomers to the world of water.
Impact of Co‐doping Eu3+ and Gd3+ in HMO‐Based Glasses for Structural and Optical Properties and Radiation Shielding Enhancement
Authors: D'Souza Ashwitha Nancy , Madivala Sumanth G. , Saraswathi A. Vidya , Sayyed M. I. , Rashad M. , Kamath Sudha D.
Published: January 2025

Eu‐Gd co‐doped glasses composed of 15B2O3–12SiO2–(40‐x)TeO2–3Eu2O3–xGd2O3–12Bi2O3–8BaO–10ZnO with x = 0–4 mol% (coded as EuGd‐x) were fabricated using melt quench approach to develop transparent radiation shielding system. Their structural, optical and mechanical properties were examined. 5.3663, 5.4264, 5.7405, 5.4683 and 5.6756 g/cm3 were the densities of EuGd‐0, EuGd‐1, EuGd‐2, EuGd‐3 and EuGd‐4, respectively. Gamma shielding ability of EuGd system was simulated using the Photon Shielding and Dosimetry software in energy spectrum 0.015–15 MeV. On co‐doping Gd3+ with Eu3+, clear advancement in gamma and neutron shielding ability was perceived; EuGd‐2 dominates because of the highest density. At 0.662 MeV, the uppermost and lowermost (0.501 and 0.468 cm−1) linear attenuation coefficients (LAC) were demonstrated by EuGd‐2 and EuGd‐0, respectively. EuGd‐2 distinguished itself with least half value layer (HVL) = 1.383 cm at 0.662 MeV, compared to EuGd‐0 (1.483 cm). Photon build‐up inside the glasses declined with Gd concentration at low gamma energies (< 2 MeV). EuGd‐2 also showcased maximum fast neutron removal (FNR) cross‐sectional value (0.10935 cm−1). Comparison between singly doped Eu2O3, Gd2O3 glasses and the current co‐doped glasses established that EuGd‐2 is the superior gamma shield in terms of LAC, HVL and effective atomic number.
A Comparison of the Optical Properties of Fibre‐Based Luminescent Solar Concentrators and Transparent Wood Towards Sustainable Waveguides
Authors: Mohan Brindha V. G. , Shobhana V. G. , Boopathi N. Manikanda
Published: January 2025

Aiming at net‐zero emissions, most international and national policies focus on sustainable development goals. Hence, there is an immediate need for replacing carbon‐intensive materials with biomaterials. In this respect, this article presents a road‐map for moving from polymeric to sustainable waveguides in optical devices. Previous reports indicate that luminescent fibres exhibit better photon concentrations of nearly 30%–33% higher than flat‐plate polymeric waveguides. It is also verified that the photon in‐out ratio increases by 3.44 times when the waveguide geometry is changed from planar to an equivalent area of fibre bundle with the same luminophore. Meanwhile, transparent wood (Twood) is gaining attention as a green alternative to acrylic sheets. The structure and function of transparent wood conforms well with the fibre‐based waveguides of luminescent solar concentrators (LSCs). Therefore, it is intriguing to compare Twood with intrinsic micro fibrillary interior with fibre‐based LSC as a natural alternative. This review provides an in‐depth analysis, emphasizing the benefits and associated challenges in using cylindrical concentrators over planar LSCs. The paper collects and compares the phenomenon of light guiding of cylindrical and fibre‐based LSCs with that of Twood. It is important to consider the key points discussed here while making a transition towards sustainable waveguides.
Fluorometric Turn Off Detection of Cu2+ and Pd2+ Ions Using 1‐(Imidazo[5,1‐a]isoquinolin‐3‐yl)naphthalen‐2‐ol
Authors: Kumar Sandeep , Phogat Hitesh , Manivannan Vadivelu
Published: January 2025

The fused heterocycle 1‐(imidazo[5,1‐a]isoquinolin‐3‐yl)naphthalen‐2‐ol (LH) has been synthesized and characterized by spectroscopic methods. Probe LH upon irradiation with λex = 336 nm exhibited strong fluorescence with λem = 437 nm in MeOH/HEPES buffer (5 mM, pH = 7.4, 2:8, v/v). Upon adding several metal ions, the fluorescence intensity was quenched only by Cu2+ and Pd2+ ions. This fluorescence turn‐off response by Cu2+ and Pd2+ ions was observed even in the coexistence of other metal ions and anions. From the Job's plot and mass spectra analysis, a 2:1 ratio of LH:M2+ was obtained, and the composition [Cu(L)2H2O] and [Pd(L)2] has been assigned. The detection limit for Cu2+ and Pd2+ ions was determined to be 0.24 and 0.35 μM, respectively, and workable pH window to be 4–10. The binding of LH to Cu2+ and Pd2+ resulted in red‐shift in the UV–visible spectrum, which was supported by DFT/TDDFT calculations.
Characterization of large transgene integrations in Chinese hamster ovary cells using a bioengineered mammalian transposase
Authors: Marx Nicolas , Otte Anna‐Maria , Leitner Klaus , Sitepu Rehmadanta , Berger Thomas , Schäpertöns Veronika , Huber Christian G. , Zhu Quan , Nema Sandeep , Higgins Joseph J. , Borth Nicole
Published: January 2025

We present the first use of a bioengineered mammalian transposase system derived from Myotis lucifugus (bMLT) for integration of expression vectors into the CHO genome, focusing on GFP and trastuzumab production. Initially, CHO‐K1 cells are transfected with a GFP reporter and varying amounts of bMLT DNA or mRNA. GFP expression is monitored over 17 weeks without selective pressure. Transfection efficiency shows around 90% GFP‐positive cells, but in control cultures GFP expression disappears after 10 days. In contrast, bMLT‐treated cultures maintain stable GFP expression, with a dose‐dependent integration efficiency of up to 60%. The highest GFP expression per cell is observed with lower bMLT amounts. Next‐generation sequencing analysis reveals multiple integration sites, with 85% correctly integrated sequences. Next, CHO‐GS−/− cells are transfected with trastuzumab and bMLT DNA or mRNA. Cells are selected in glutamine‐free medium with varying methionine sulfoximine (MSX) concentrations. Recovery is faster without MSX, and no difference is observed between bMLT DNA and mRNA transfections. bMLT‐treated cultures show a higher percentage of trastuzumab‐secreting cells (40%–55%) compared with random integration (0.3%–0.5%). The absence of insulators in the trastuzumab plasmid likely affects selection behavior, as integration in heterochromatic regions results in gene repression. Overall, bMLT‐mediated integration proves efficient, generating stable cell pools with high expression profiles without selective pressure. The integration sites' genomic location significantly impacts productivity, with favorable regions supporting higher expression. This method shows promise for the rapid and efficient generation of high‐producing cell lines and for rapid evaluation of long‐term effects of different cell engineering approaches.
Deciphering the Differences Between Epstein–Barr Virus‐Associated and Negative Gastric Cancer in the Prospect of CDKN2A Genomic Alterations and Lymphoid Infiltration
Authors: Xie Fuda , Chen Bonan , Lyu Yang , Yu Peiyao , Fang Canbin , Leung Kam Tong , Wang Shouyu , Xu Dazhi , Yu Jun , Lo Kwok Wai , To Ka Fai , Kang Wei
Published: January 2025

Background

Gastric cancer (GC) is a major health concern worldwide. One important contributing factor is the presence of the Epstein‐Barr virus (EBV). However, the molecular pattern of how EBV participates in the malignant transition process remains unclear.

Methods

GC samples were stained by immunohistochemistry, fluorescent and EBV‐encoded small RNA in situ hybridization to identify CD8 expression, CDKN2A genomic alteration, and EBV existence. Functional potentials of EBV infection were predicted by bioinformatic enrichment analysis.

Results

CDKN2A genestayed intact in all EBV‐associated GC cases. Meanwhile, CDKN2A deletion (8.43% cases) was exclusive to EBV‐negative GC cases. Furthermore, EBV infection was positively correlated with CD8+T cell infiltration, and both of them predicted better prognosis.

Conclusion

This study highlighted the comprehensive impact of EBV infection in GC formation and proposed a thought‐provoking observation for further investigation into the roles of CDKN2A and EBV infection in gastric tumorigenesis.
Characterization and Detection Strategy Exploration in Cryptogenic Hepatocellular Carcinoma: Insights From a Super‐Aged Region in Japan
Authors: Sugihara Takaaki , Nagahara Takakazu , Kihara Takuya , Ikeda Suguru , Hoshino Yoshiki , Matsuki Yukako , Sakaguchi Takuki , Kurumi Hiroki , Onoyama Takumi , Takata Tomoaki , Matono Tomomitsu , Isomoto Hajime
Published: January 2025

Background and Aim

In recent years, there has been a rise in cryptogenic hepatocellular carcinoma (c‐HCC) cases in Japan, posing a detection challenge due to an unknown etiology. This study aims to enhance diagnostic strategies for c‐HCC by analyzing its characteristics and exploring current opportunities for detection.

Methods

A retrospective study was conducted from April 2012 to March 2022, enrolling 372 newly diagnosed hepatocellular carcinoma (HCC) patients. Excluding cases associated with hepatitis viral infection, alcoholic liver disease, non‐alcoholic fatty liver disease/steatohepatitis, autoimmune hepatitis, primary biliary cholangitis, and congestive hepatopathy, the study specifically focused on genuine c‐HCC. The analysis delved into the characteristics, detection opportunities, and survival outcomes associated with c‐HCC.

Results

Among the non‐viral HCC cases, 55 patients (29.3%) (34 men and 21 women) were diagnosed with c‐HCC, making it the second‐highest etiology. Notably, individuals with c‐HCC, typically aged 60 and above (median age 76.0), exhibited a women predominance and presented with larger tumors (4.5 cm vs. 2.5 cm), correlating with a poorer prognosis. Cirrhosis was notably absent in most c‐HCC cases (72.7%), and more than half (56.4%) did not have diabetes mellitus (DM). Diagnostic pathways for c‐HCC primarily involved incidental imaging (47%) and symptoms (24%). Within the cohort of c‐HCC, the prognosis for symptomatic cases is notably unfavorable compared to other cases [median survival time 19.0 (7.0–45.0) months vs. 47.0 (29.0–76.0) months, p = 0.029]. In the multivariate regression analysis, age and women emerged as independent factors associated with c‐HCC. Rather than a significant increase in women, there is a narrowing gender gap.

Conclusion

Patients with c‐HCC were predominantly elderly, without cirrhosis or diabetes, and exhibited minimal gender differences. Detection often occurred incidentally through abdominal imaging. Considering the limitations of conventional surveillance, it seems reasonable to propose that abdominal imaging be included in cancer screening, particularly for individuals aged 60 and older.

Trial Registration

1610A127
Unveiling Cannabinoids and Terpenes Diversity in Cannabis sativa L. From Northern India for Future Breeding Strategies
Authors: Ghosh Dipayan , Kundu Anitika , Chaudhary Neha , Gupta Darshan , Dwivedi Mridula , Verma Ram Swaroop , Shanker Karuna , Kumar Birendra , Kumar Narendra
Published: January 2025

Cannabis sativa L. is an important medicinal plant with high commercial value. In recent years, the research interest in cannabidiol (CBD) and terpene‐rich cannabis has been rapidly expanding due to their high therapeutic potential. The present study aims to explore the phytocannabinoids and terpenes diversity in C. sativa collected from different parts of northern India. Our findings revealed that the cannabinoids and terpenes synthesize together in capitate stalked and capitate sessile glandular trichomes, whereas bulbous glands synthesize only terpenes. The North Indian C. sativa is mainly dominated by tetrahydrocannabinol. The CBD‐rich plant diversity is nominal (1.11%) in studied north Indian C. sativa. The essential oil profiling reveals (E)‐caryophyllene (10.30%–36.80%) as the major constituent, followed by α‐humulene (0.50%–15.29%) and α‐bisabolol (0.00%–16.40%) in the North Indian population. The cannabinoids and terpenes content showed significant diversity among and within the five studied populations. The correlation analysis between cannabinoids and terpenes indicates that α‐pinene, β‐pinene and limonene positively correlated with CBD content. Similarly, α‐ and β‐selinene correlate positively with tetrahydrocannabinolic acid content. This study could help to identify the key cultivars from India and establish a consistent chemotype for future breeding programs.
Synthesis, Characterization, Anti‐Nematicidal, and Computational Study of Copper(II) Complex Derived From Fluoro‐substituted Schiff Base Ligand
Authors: Lawan Salisu Y. , Ndahi Naomi P. , Galadima Ibrahim B. , Wahab Olaide O. , Yusuf Tunde L. , Coetzee Louis‐Charl C. , El‐Maksoud Mostafa S. Abd , Waziri Ibrahim
Published: January 2025

In this study, a novel fluoro‐substituted Schiff base ligand (HL) was synthesized through a condensation reaction between 2‐bromo‐4‐(trifluoromethoxy)aniline and 2‐hydroxybenzaldehyde in methanol solvent at room temperature. The ligand was subsequently reacted with copper(II) acetate to produce the corresponding Cu(II) complex (CuL2). Both the ligand and its complex underwent characterization using various techniques including nuclear magnetic resonance, ultraviolet‐visible, Fourier‐transform infrared, thermogravimetric analysis, elemental analysis, and mass spectroscopy. In addition, the solid‐state structure of the complex was determined through single crystal X‐ray diffraction analysis, confirming the successful isolation of the compounds. Subsequently, the nematicidal activities of the ligand and its complex were assessed through in vitro egg hatching inhibition and mortality rate assays, in comparison to the control, carbofuran (Crf), at concentrations of 50 and 100 µM over a 24–72‐h period. The results indicated the ligand's superiority over the complex in both assays at lower concentrations. At a concentration of 50 µM, the ligand HL demonstrated 100% egg‐hatching inhibition at 24, 48, and 72 h, whereas the complex CuL2 showed egg‐hatching inhibition rates of 93.86 ± 0.22%, 98.76 ± 0.14%, and 99.33 ± 0.52% at the same time intervals. The control, Crf, exhibited inhibition rates of 56.33 ± 0.33%, 69.94 ± 0.6%, and 67.00 ± 0.34% over the same time period. Similarly, at a concentration of 100 µM, both the ligand and complex demonstrated 100% egg‐hatching inhibition at 24, 48, and 72 h, while the control showed egg‐hatching rates of 88.16 ± 0.84%, 89.9 ± 0.55%, and 90.8 ± 0.50%. Regarding the mortality rate, at 50 and 100 µM, the ligand HL exhibited a 100% mortality rate within 24 to 72 h, whereas the complex CuL2 displayed mortality rates of 56.66 ± 0.33%, 63.3 ± 0.23%, and 86.66 ± 0.13% at 24, 48, and 72 h, respectively, with a mortality rate of 100% at 100 µM within the same time intervals. The control, Crf, demonstrated mortality rates of 54%–67% at 50 µM and 62%–78% at 100 µM within 24–72 h. Additionally, the density‐functional theory study revealed the electronic properties of the compounds, reinforcing the experimental findings.
Enhanced Carbon Dioxide Capture: Adsorption and Physicochemical Properties of SBA‐15 Mesoporous Silica
Authors: Mahendran Shalini , Yahaya Noorfatimah , Hameed Bassim H. , Vo Dai Viet N. , Ouakouak Abdelkader , Nishiyama Norikazu , Mohd Din Azam Taufik
Published: January 2025

Global warming is widely recognized as one of humanity's most urgent challenges, making CO2 capture from the environment crucial to mitigating problems associated with climate change. In this study, ordered mesoporous silica SBA‐15 was synthesized using the sol–gel process with Pluronic P123, a nonionic surfactant, and tetraethyl orthosilicate as the silica source, with hydrochloric acid serving as the catalyst. The results indicated that the CO2 adsorption capacity of SBA‐15 was improved with higher CO2 feed concentration but decreased with increasing flowrate, temperature, and adsorbent loading. The Avrami model provided the best fit for the experimental kinetic data. The Thomas and Yoon–Nelson models were successful in predicting the CO2 adsorption performance of SBA‐15 in the fixed‐bed column system. The synthesized SBA‐15 demonstrated its significant potential as a cost‐effective CO2 adsorbent by maintaining a high adsorption capacity, even after multiple regeneration cycles.
Amino‐Substituted Azoxybenzenes as Potential Redox‐Active Catholyte Materials
Authors: Schatz Dominic , Burdenski Chris , Schneider Finn M. , Hansmann Max M. , Wegner Hermann A.
Published: January 2025

Aryl diazenes, particularly azobenzenes (AB), represent a versatile class of compounds with significant historical and practical relevance, ranging from dyes to molecular machines, solar thermal and electrochemical storage. Their oxygen‐substituted counterparts, azoxybenzenes (AOB), share structural similarities but have been less explored, especially in energy storage applications. This study investigates the redox properties of AOB, comparing them to AB, and evaluates their potential as redox‐active materials for energy storage systems. Through cyclic voltammetry (CV) and spectro‐electrochemical analyses, we demonstrate that AOBs exhibit a distinct redox behaviour, influenced by the solvent and electrolyte environment, with a reversible oxidation process. Despite their promising redox characteristics, AOBs suffer from capacity decay during galvanostatic cycling, likely due to the instability of the radical cation intermediate. These findings suggest that while AOBs offer intriguing redox properties, further investigation into stabilization strategies are needed for their application in energy storage.
Organometallic‐polypeptide Block Copolymers: Synthesis and Crystallization‐driven Self‐assembly in Aqueous Solutions to Rod‐like and Plate‐like Micelles with Polypeptide Coronas
Authors: Wang Yishan , Taek Kim Kyoung , Manners Ian , Winnik Mitchell A.
Published: January 2025

The synthesis of polyferrocenyldimethylsilane‐b‐poly(L‐glutamic acid) block copolymers was systematically explored. Rod‐like and plate‐like micelles were prepared from self‐assembly of the block copolymers in aqueous solution with two different approaches. In a dissolution‐dialysis approach, micelles were prepared by dissolving a block copolymer sample in excess aqueous base followed by the dialysis of the solution against water. The morphology of the resultant micelles showed composition dependence. The block copolymer sample with the lowest soluble block content formed rod‐like micelles, while the other samples with higher soluble block content formed spherical micelles. In a THF‐mediated approach, THF was added into a block copolymer solution, which was first prepared by the dissolution‐dialysis approach, and then the THF was evaporated slowly. Plate‐like micelles were obtained from all the block copolymer samples examined, and these had a broad range of soluble block content. The formation of these plate‐like micelles was attributed to the crystallization of the PFDMS blocks in the presence of THF. A tendency of large platelet micelles evolving to thin filaments over time was observed. This change may have been driven by the increase in the corona‐chain stretching energy as THF evaporated.
Carbene‐Functionalized Bulky‐Cyclopentadiene Rings
Authors: Arumugam Selvakumar , Kushvaha Saroj Kumar , Ravichandran Prathap , Kumar Jayasree , Gorantla Sai Manoj N. V. T. , Mondal Totan , Roesky Herbert W. , Mondal Kartik Chandra
Published: January 2025

A series of significantly bulky mono‐ and di‐substituted cyclic alkyl‐amino carbene (cAAC)‐ functionalized cyclopentadiene ring (Cp) compounds were synthesized. The functionalization of the Cp ring with cAAC ligands makes them significantly bulkier, while retaining their ligation properties. These compounds display interesting fluorescence properties. In these compounds, intra‐molecular charge transfer is observed from electron‐rich carbene to electron‐deficient cyclopentadiene unit. These high yielding compounds have been characterized by X‐ray single‐crystal diffraction and their emission properties have been studied. Rotational conformers (via C−C bond rotation) play a pivotal role with possible different extent of intramolecular charge‐transfer (ICT) from carbene to cyclopentadiene ring. Variable temperature‐dependent NMR studies were performed along with NOSY, COSY and different 2D NMR techniques to estimate the energy barriers and 1,5‐Hydrogen shift.
Carbamate‐Functionalized NLOphores via a Formal [2+2] Cycloaddition‐Retroelectrocyclization Strategy
Authors: Savaş İpek , Çelik Mehmet Efe , Barsella Alberto , Dengiz Cagatay
Published: January 2025

This study introduces a new donor group capable of activating click‐type [2+2] cycloaddition‐retroelectrocyclizations, generally known for their limited scope. Target chromophores were synthesized using isocyanate‐free urethane synthesis. The developed synthetic method allows for the tuning of the optical properties of the chromophores by modifying the donor groups, the acceptor units, and the side chains. The charge transfer (CT) bands of the chromophores exhibit λmax values ranging from 363 to 692 nm. The CT bands observed have been supported by solvatochromism and protonation experiments. The synthesized compounds exhibit positive solvatochromism. Due to their potential as NLOphore candidates, the stability of the synthesized compounds have been investigated both experimentally through TGA and theoretically by calculating parameters such as frontier orbital energy differences, electronegativity, and global hardness/softness. TD‐DFT calculations were used to elucidate the nature of the electronic transitions, revealing that the bands correspond to CT arising from HOMO‐to‐LUMO excitations. The NLO properties of the chromophores were investigated theoretically by DFT methods and experimentally by the EFISHG technique. Both results are shown to be in agreement with HOMO‐LUMO energy differences. The experimental μβ values of the selected molecules range from 470×10−48 to 5400×10−48 esu.
Creating Dual Active Sites in Ru‐doped FeMn‐MOF‐74 for Efficient Overall Water Splitting
Authors: Sun Wenting , Hu Jinqi , Lou Yongbin , Chen Jinxi
Published: January 2025

The design of well‐engineered bifunctional electrocatalysts is crucial for achieving durable and efficient performance in overall water splitting. In this study, Ru‐doped FeMn‐MOF‐74 itself has Ru sites and generates FeMnOOH under catalytic conditions, forming dual active sites for overall water splitting. Density functional theory (DFT) calculations demonstrate that the Ru dopants exhibit optimized binding strength for H* and enhanced hydrogen evolution reaction (HER) performance. Moreover, the Mn sites within FeMnOOH lower the energy barrier for the rate‐determining step (from O* to OOH*), serving as the active centre for oxygen evolution reaction (OER). The incorporation of Ru significantly improves the electron transfer properties of FeMn‐MOF‐74 and enhances its water adsorption capacity, synergistically boosting its bifunctional activity. This strategy of designing dual active sites provides new insights into the development of bifunctional metal‐organic frameworks (MOFs) for efficient overall water splitting.
Seeded Growth and Scintillation Properties of Cs3Cu2I5 Perovskite Crystals by the Vertical Bridgman Method
Authors: Gu Yankai , Liu Yongsheng , Li Yang , Huang Yexi , Shen Hui , Xu Jiayue
Published: January 2025

Copper halide perovskite Cs3Cu2I5 has attracted great interest due to its excellent scintillation properties, while it is rather challenging to grow large‐size bulk crystals. Herein, the seeded growth of Cs3Cu2I5 crystals are investigated by the vertical Bridgman method. Initially, Cs3Cu2I5 crystal is grown by spontaneous nucleation in a sealed quartz tube. Some Cs3Cu2I5 grains are processed into cylinders for the following seeded growth. Black Cs3Cu2I5 bulk crystal is obtained from the Pt crucible with a seed well in the air, with a dimension of Φ25 mm × 60mm and a <131> preferred growth orientation. The existence of I2 is possibly contributed to the crystal blackening. Using isodiametric seed, transparent Cs3Cu2I5 crystal wafers with dimensions over 20 mm are successfully grown under vacuum. The absorption edge of the Cs3Cu2I5 crystal is located at ≈330 nm. The photoluminescence of the crystal is centered at 445 nm, featuring a primary decay time of 850.88 ns (83.76%). It displays a significant light yield of 37,000 photons per MeV and an energy resolution of 5.1% at 662 keV, when subjected to γ‐ray radiation. The results reveal the feasibility of seeded growth of Cs3Cu2I5 crystals for potential scintillation applications.
Vitamin K‐dependent gamma‐carboxyglutamic acid protein 1 promotes pancreatic ductal adenocarcinoma progression through stabilizing oncoprotein KRAS and tyrosine kinase receptor EGFR
Authors: Wu Zheng , Ye Qing , Zhang Shan , Hu Li‐Peng , Wang Xiao‐Qi , Yao Lin‐Li , Zhu Lei , Xiao Shu‐Yu , Duan Zong‐Hao , Zhang Xue‐Li , Jiang Shu‐Heng , Zhang Zhi‐Gang , Liu De‐Jun , Li Dong‐Xue , Yang Xiao‐Mei
Published: January 2025

Background

Vitamin K‐dependent γ‐glutamic acid carboxylation (Gla) proteins are calcium‐binding and membrane‐associated, participating in coagulation, bone turnover, and cancer biology. The molecular function of transmembrane proline‐rich Gla proteins (PRRGs) remains unexplored.

Methods

Analysis of pancreatic ductal adenocarcinoma (PDAC) datasets, including transcription profiles, clinical data, and tissue microarrays, was conducted to evaluate PRRG1 expression and its clinical relevance. PDAC cell lines with overexpressed, knockdown, and mutated PRRG1 were developed to study biological functions and pathways using RNA‐seq, co‐immunoprecipitation with mass spectrometry, Western blotting, and immunofluorescence. In vivo xenograft and orthotopic models assessed PRRG1's impact on PDAC progression, with and without warfarin treatment.

Results

PRRG1 was significantly upregulated in PDAC compared to normal pancreas, correlating with poorer patient survival. PRRG1 knockdown reduced PDAC cell proliferation, anchorage‐independent growth in vitro, and tumor growth in vivo. PRRG1 localized at the plasma membrane, interacted with the HECT E3 ligase NEDD4 via the C‐terminal PPXY motif, and promoted NEDD4 self‐ubiquitination, reducing its protein levels. PRRG1 knockdown elevated NEDD4, destabilizing the oncoprotein KRAS and receptor EGFR, and attenuating downstream signaling and macropinocytosis under nutrient deprivation. The vitamin K‐dependent Gla modification of PRRG1 was crucial for its membrane localization and pro‐tumorigenic effects, and was inhibited by low‐dose warfarin, a clinical vitamin K antagonist.

Conclusions

This study identifies PRRG1 as a key regulator of pro‐tumorigenic signaling in PDAC, suggesting the potential of repurposing the anticoagulant warfarin as a therapeutic strategy.

Key points

PRRG1 is identified as the transmembrane Gla protein mediating PDAC malignancy.

PRRG1 recruits and induces self‐ubiquitination of membrane‐anchoring E3 ligase NEDD4.

PRRG1 exerts a protective role toward KRAS and EGFR by inhibiting NEDD4.

The anticoagulant warfarin can be utilized to inhibit PRRG1 and PDAC advancement.
An Enhanced Heterogeneous Local Directed Acyclic Graph Blockchain With Recalling Enhanced Recurrent Neural Networks for Routing in Secure MANET‐IOT Environments in 6G
Authors: Begum M. Baritha , Suganthi B. , Sivagamasundhari P. , Arunmozhi S. A. , Suhail S. J. Muhamed
Published: January 2025

Mobile ad hoc networks (MANETs) integrated with the Internet of Things (IoT) form a decentralized communication framework crucial for 6G environments. However, ensuring secure and efficient routing in such networks remains a challenge due to their distributed nature and vulnerability to attacks. This paper introduces a heterogeneous local directed acyclic graph blockchain (HLDAG‐BC) combined with recalling enhanced recurrent neural networks (RERNNs) for secure and efficient routing in MANET‐IoT environments. The HLDAG‐BC offers tamper‐proof communication and identity‐based conditional privacy‐preserving authentication (ICPA) is a lightweight and secure node authentication scheme. Network nodes are grouped using the kernel neutrosophic c‐means (KNCM) algorithm. The optimal cluster heads are chosen using the red piranha optimization (RPO) method. RERNN determines the shortest routing path to increase reliability and minimize latency. Furthermore, an HDLNN is used for intrusion detection to achieve robust network security. The HLDAG‐BC‐RERNN approach proposed shows that the packet delivery ratio improves by 31.35%, throughput by 34.56%, latency by 30.29%, and network lifetime by 28.67% compared to the existing approaches, as shown in the comprehensive evaluations. In conclusion, the proposed framework offers a scalable and secure solution for MANET‐IoT networks, making it a viable approach for future 6G applications.
Putting seedlings on the map: Trade‐offs in demographic rates between ontogenetic size classes in five tropical forests
Authors: Kambach Stephan , Bruelheide Helge , Comita Liza S. , Condit Richard , Wright S. Joseph , Aguilar Salomón , Chang‐Yang Chia‐Hao , Chen Yu‐Yun , Garwood Nancy C. , Hubbell Stephen P. , Luo Pei‐Jen , Metz Margaret R. , Nasardin Musalmah Bt. , Pérez Rolando , Queenborough Simon A. , Sun I‐Fang , Swenson Nathan G. , Thompson Jill , Uriarte María , Valencia Renato , Yao Tze Leong , Zimmerman Jess K. , Rüger Nadja
Published: January 2025

All species must partition resources among the processes that underly growth, survival, and reproduction. The resulting demographic trade‐offs constrain the range of viable life‐history strategies and are hypothesized to promote local coexistence. Tropical forests pose ideal systems to study demographic trade‐offs as they have a high diversity of coexisting tree species whose life‐history strategies tend to align along two orthogonal axes of variation: a growth–survival trade‐off that separates species with fast growth from species with high survival and a stature–recruitment trade‐off that separates species that achieve large stature from species with high recruitment. As these trade‐offs have typically been explored for trees ≥1 cm dbh, it is unclear how species' growth and survival during earliest seedling stages are related to the trade‐offs for trees ≥1 cm dbh. Here, we used principal components and correlation analyses to (1) determine the main demographic trade‐offs among seed‐to‐seedling transition rates and growth and survival rates from the seedling to overstory size classes of 1188 tree species from large‐scale forest dynamics plots in Panama, Puerto Rico, Ecuador, Taiwan, and Malaysia and (2) quantify the predictive power of maximum dbh, wood density, seed mass, and specific leaf area for species' position along these demographic trade‐off gradients. In four out of five forests, the growth–survival trade‐off was the most important demographic trade‐off and encompassed growth and survival of both seedlings and trees ≥1 cm dbh. The second most important trade‐off separated species with relatively fast growth and high survival at the seedling stage from species with relatively fast growth and high survival ≥1 cm dbh. The relationship between seed‐to‐seedling transition rates and these two trade‐off aces differed between sites. All four traits were significant predictors for species' position along the two trade‐off gradients, albeit with varying importance. We concluded that, after accounting for the species' position along the growth–survival trade‐off, tree species tend to trade off growth and survival at the seedling with later life stages. This ontogenetic trade‐off offers a mechanistic explanation for the stature–recruitment trade‐off that constitutes an additional ontogenetic dimension of life‐history variation in species‐rich ecosystems.
Seagrass wasting disease prevalence and lesion area increase with invertebrate grazing across the northeastern Pacific
Authors: Aoki Lillian R. , Ritter Carmen J. , Beatty Deanna S. , Domke Lia K. , Eckert Ginny L. , Graham Olivia J. , Gomes Carla P. , Gross Collin , Hawthorne Timothy L. , Heery Eliza , Hessing‐Lewis Margot , Hovel Kevin , Koehler Karl , Monteith Zachary L. , Mueller Ryan S. , Olson Angeleen M. , Prentice Carolyn , Rappazzo Brendan , Stachowicz John J. , Tomas Fiona , Yang Bo , Harvell C. Drew , Duffy J. Emmett
Published: January 2025

Disease is a key driver of community and ecosystem structure, especially when it strikes foundation species. In the widespread marine foundation species eelgrass (Zostera marina), outbreaks of wasting disease have caused large‐scale meadow collapse in the past, and the causative pathogen, Labyrinthula zosterae, is commonly found in meadows globally. Research to date has mainly focused on abiotic environmental drivers of seagrass wasting disease, but there is strong evidence from other systems that biotic interactions such as herbivory can facilitate plant diseases. How biotic interactions influence seagrass wasting disease in the field is unknown but is potentially important for understanding dynamics of this globally valuable and declining habitat. Here, we investigated links between epifaunal grazers and seagrass wasting disease using a latitudinal field study across 32 eelgrass meadows distributed from southeastern Alaska to southern California. From 2019 to 2021, we conducted annual surveys to assess eelgrass shoot density, morphology, epifauna community, and the prevalence and lesion area of wasting disease infections. We integrated field data with satellite measurements of sea surface temperature and used structural equation modeling to test the magnitude and direction of possible drivers of wasting disease. Our results show that grazing by small invertebrates was associated with a 29% increase in prevalence of wasting disease infections and that both the prevalence and lesion area of disease increased with total epifauna abundances. Furthermore, these relationships differed among taxa; disease levels increased with snail (Lacuna spp.) and idoteid isopod abundances but were not related to abundance of ampithoid amphipods. This field study across 23° of latitude suggests a prominent role for invertebrate consumers in facilitating disease outbreaks with potentially large impacts on coastal seagrass ecosystems.