bluuebunny/crossref_metadata_2025 huggingface dataset:
The Enormous Potential of Sodium/Potassium‐Ion Batteries as the Mainstream Energy Storage Technology for Large‐Scale Commercial Applications
Authors: Gao Yanjun , Yu Qiyao , Yang Huize , Zhang Jianguo , Wang Wei
Published: June 2024

Cost‐effectiveness plays a decisive role in sustainable operating of rechargeable batteries. As such, the low cost‐consumption of sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs) provides a promising direction for “how do SIBs/PIBs replace Li‐ion batteries (LIBs) counterparts” based on their resource abundance and advanced electrochemical performance. To rationalize the SIBs/PIBs technologies as alternatives to LIBs from the unit energy cost perspective, this review gives the specific criteria for their energy density at possible electrode‐price grades and various battery‐longevity levels. The cost ($ kWh−1 cycle−1) advantage of SIBs/PIBs is ascertained by the cheap raw‐material compensation for the cycle performance deficiency and the energy density gap with LIBs. Furthermore, the cost comparison between SIBs and PIBs, especially on cost per kWh and per cycle, is also involved. This review explicitly manifests the practicability and cost‐effectiveness toward SIBs are superior to PIBs whose commercialization has so far been hindered by low energy density. Even so, the huge potential on sustainability of PIBs, to outperform SIBs, as the mainstream energy storage technology is revealed as long as PIBs achieve long cycle life or enhanced energy density, the related outlook of which is proceeded as the next development directions for commercial applications.
Blue‐Emitting Boron‐ and Nitrogen‐Doped Carbon Dots for White Light‐Emitting Electrochemical Cells
Authors: Cavinato Luca M. , Kost Veronika , Campos‐Jara Sergi , Ferrara Sara , Chowdhury Sanchari , Groot Irene M.N. , Da Ros Tatiana , Costa Rubén D.
Published: June 2024

This work describes the first use of blue‐emitting boron‐ and nitrogen‐doped carbon dots (BN‐CDs), rationalizing their photoluminescence behavior in solution and ion‐based thin‐films to prepare white light‐emitting electrochemical cells (LECs). In detail, a cost‐effective and scalable water‐based microwave‐assisted synthesis procedure is set for BN‐CDs featuring an amorphous carbon‐core doped with N and B. While they show a bright (photoluminescence quantum yield of 42%) and excitation‐independent blue‐emission (440 nm) in solution related to emitting n−π* surface states, they are not emissive in thin‐films due to aggregation‐induced quenching. Upon fine‐tuning the film composition (ion‐based host), an excitation dependent emission covering the whole visible range is noted caused by interaction of the ion electrolyte with the peripheral functionalization of the BN‐CDs. Moreover, the efficient energy transfer from the host to the BN‐CDs emitting species enabled good performing LECs with white emission (x/y CIE coordinates of 0.30/0.35, correlated color temperature of 6795 K, color rendering index of 87) and maximum luminance of 40 cd m−2, and stabilities of a few hours. This represents a significant improvement compared to the prior‐art monochromatic CD‐based LECs with similar brightness levels, but stabilities of <1 min.
The Rise of 2D Materials‐Based Photoelectrochemical Photodetectors: Progress and Prospect
Authors: Zhou Junxin , Zhang Nana , Liu Jiaming , Gao Qiyue , Zhang Yuan , Gao Feng , Hu PingAn , Feng Wei
Published: June 2024

2D materials have garnered significant research attention due to their unique electrical and optical properties. Various photodetectors (PDs) based on 2D materials have been demonstrated to possess a high photoresponse, achieve specific light detection, and construct flexible devices. Among these, photoelectrochemical‐type (PEC) PDs are attracting increasing attention due to their facile fabrication processes, self‐powered capability, and high sensitivity. Compared with transitional solid‐state PDs based on 2D materials, research on 2D material‐based PEC PDs is still in its initial stages but exhibits promising potential for various applications. This paper comprehensively reviews recent advancements in 2D material‐based PEC PDs. The 2D materials for PEC PDs are first classified, and then the synthesis methods employed for their fabrication are briefly summarized. Later, the performance and performance optimization strategies of various 2D material‐based PEC PDs are discussed. Finally, the challenges and opportunities for developing high‐performance 2D material‐based PEC PDs are highlighted.
E3 Ubiquitin Ligase RNF13 Suppresses TLR Lysosomal Degradation by Promoting LAMP‐1 Proteasomal Degradation
Authors: Liu Wei , Wang Yuyang , Liu Shuo , Zhang Xuan , Cao Xuetao , Jiang Minghong
Published: June 2024

As a highly organized system, endo‐lysosomes play a crucial role in maintaining immune homeostasis. However, the mechanisms involved in regulating endo‐lysosome progression and subsequent inflammatory responses are not fully understood. By screening 103 E3 ubiquitin ligases in regulating endo‐lysosomal acidification, it is discovered that lysosomal RNF13 inhibits lysosome maturation and promotes inflammatory responses mediated by endosomal Toll‐like receptors (TLRs) in macrophages. Mechanistically, RNF13 mediates K48‐linked polyubiquitination of LAMP‐1 at residue K128 for proteasomal degradation. Upon TLRs activation, LAMP‐1 promotes lysosomes maturation, which accelerates lysosomal degradation of TLRs and reduces TLR signaling in macrophages. Furthermore, peripheral blood mononuclear cells (PBMCs) from patients with rheumatoid arthritis (RA) show increased RNF13 levels and decreased LAMP‐1 expression. Accordingly, the immunosuppressive agent hydroxychloroquine (HCQ) can increase the polyubiquitination of RNF13. Taken together, the study establishes a linkage between proteasomal and lysosomal degradation mechanisms for the induction of appropriate innate immune response, and offers a promising approach for the treatment of inflammatory diseases by targeting intracellular TLRs.
A Glucose‐Responsive Hydrogel Inhibits Primary and Secondary BRB Injury for Retinal Microenvironment Remodeling in Diabetic Retinopathy
Authors: Zhou Yue , Zhao Chan , Shi Zhiyuan , Heger Zbynek , Jing HuaQing , Shi Zhengming , Dou Yunsheng , Wang Siyu , Qiu Zitong , Li Nan
Published: June 2024

Current diabetic retinopathy (DR) treatment involves blood glucose regulation combined with laser photocoagulation or intravitreal injection of vascular endothelial growth factor (VEGF) antibodies. However, due to the complex pathogenesis and cross‐interference of multiple biochemical pathways, these interventions cannot block disease progression. Recognizing the critical role of the retinal microenvironment (RME) in DR, it is hypothesized that reshaping the RME by simultaneously inhibiting primary and secondary blood–retinal barrier (BRB) injury can attenuate DR. For this, a glucose‐responsive hydrogel named Cu‐PEI/siMyD88@GEMA‐Con A (CSGC) is developed that effectively delivers Cu‐PEI/siMyD88 nanoparticles (NPs) to the retinal pigment epithelium (RPE). The Cu‐PEI NPs act as antioxidant enzymes, scavenging ROS and inhibiting RPE pyroptosis, ultimately blocking primary BRB injury by reducing microglial activation and Th1 differentiation. Simultaneously, MyD88 expression silence in combination with the Cu‐PEI NPs decreases IL‐18 production, synergistically reduces VEGF levels, and enhances tight junction proteins expression, thus blocking secondary BRB injury. In summary, via remodeling the RME, the CSGC hydrogel has the potential to disrupt the detrimental cycle of cross‐interference between primary and secondary BRB injury, providing a promising therapeutic strategy for DR.
Allicin‒Decorated FeO1‐xOH Nanocatalytic Medicine for Fe2+/Fe3+ Cycling‒Promoted Efficient and Sustained Tumor Regression
Authors: Jie Zhongming , Xiong Bingyan , Shi Jianlin
Published: June 2024

In the tumor treatment by Fenton reaction‒based nanocatalytic medicines, the gradual consumption of Fe(II) ions greatly reduces the production of hydroxyl radicals, one of the most active reactive oxygen species (ROS), leading to much deteriorated therapeutic efficacy. Meanwhile, the ROS consumption caused by the highly expressed reduced glutathione (GSH) in the tumor microenvironment further prevents tumor apoptosis. Therefore, using the highly expressed GSH in tumor tissue to promote the Fe(III) reduction to Fe(II) can not only weaken the resistance of tumor to ROS attack, but also generate enough Fe(II) to accelerate the Fenton reaction. In view of this, an allicin‒modified FeO1‐xOH nanocatalyst possessing varied valence states (II, III) has been designed and synthesized. The coexistence of Fe(II)/Fe(III) enables the simultaneous occurrence of Fenton reaction and GSH oxidation, and the Fe(III) reduction by GSH oxidation results in the promoted cyclic conversion of Fe ions in tumor and positive catalytic therapeutic effects. Moreover, allicin capable of regulating cell cycle and suppressing tumor growth is loaded on FeO1‐xOH nanosheets to activate immune response against tumors and inhibit tumor recurrence, finally achieving the tumor regression efficiently and sustainably. This therapeutic strategy provides an innovative approach to formulate efficient antitumor nanomedicine for enhanced tumor treatment.
Enhancing 2D Photonics and Optoelectronics with Artificial Microstructures
Authors: Song Haizeng , Chen Shuai , Sun Xueqian , Cui Yichun , Yildirim Tanju , Kang Jian , Yang Shunshun , Yang Fan , Lu Yuerui , Zhang Linglong
Published: June 2024

By modulating subwavelength structures and integrating functional materials, 2D artificial microstructures (2D AMs), including heterostructures, superlattices, metasurfaces and microcavities, offer a powerful platform for significant manipulation of light fields and functions. These structures hold great promise in high‐performance and highly integrated optoelectronic devices. However, a comprehensive summary of 2D AMs remains elusive for photonics and optoelectronics. This review focuses on the latest breakthroughs in 2D AM devices, categorized into electronic devices, photonic devices, and optoelectronic devices. The control of electronic and optical properties through tuning twisted angles is discussed. Some typical strategies that enhance light‐matter interactions are introduced, covering the integration of 2D materials with external photonic structures and intrinsic polaritonic resonances. Additionally, the influences of external stimuli, such as vertical electric fields, enhanced optical fields and plasmonic confinements, on optoelectronic properties is analysed. The integrations of these devices are also thoroughly addressed. Challenges and future perspectives are summarized to stimulate research and development of 2D AMs for future photonics and optoelectronics.
Phase Transformations Driving Biaxial Stress Reduction During Wake‐Up of Ferroelectric Hafnium Zirconium Oxide Thin Films
Authors: Jaszewski Samantha T. , Fields Shelby S. , Calderon Sebastian , Aronson Benjamin L. , Beechem Thomas E. , Kelley Kyle P. , Zhang Casey , Lenox Megan K. , Brummel Ian A. , Dickey Elizabeth C. , Ihlefeld Jon F.
Published: June 2024

Biaxial stress is identified to play an important role in the polar orthorhombic phase stability in hafnium oxide‐based ferroelectric thin films. However, the stress state during various stages of wake‐up has not yet been quantified. In this work, the stress evolution with field cycling in hafnium zirconium oxide capacitors is evaluated. The remanent polarization of a 20 nm thick hafnium zirconium oxide thin film increases from 9.80 to 15.0 µC cm−2 following 106 field cycles. This increase in remanent polarization is accompanied by a decrease in relative permittivity that indicates that a phase transformation has occurred. The presence of a phase transformation is supported by nano‐Fourier transform infrared spectroscopy measurements and scanning transmission electron microscopy that show an increase in ferroelectric phase content following wake‐up. The stress of individual devices field cycled between pristine and 106 cycles is quantified using the sin2(ψ) technique, and the biaxial stress is observed to decrease from 4.3 ± 0.2 to 3.2 ± 0.3 GPa. The decrease in stress is attributed, in part, to a phase transformation from the antipolar Pbca phase to the ferroelectric Pca21 phase. This work provides new insight into the mechanisms controlling and/or accompanying polarization wake‐up in hafnium oxide‐based ferroelectrics.
Scaffold‐free three‐dimensional cartilage regeneration based on cartilaginous organoids bioassembly technology
Authors: Huo Yingying , Ci Zheng , Wu Shiqi , Feng Shaoqing , Sun Yuyan , Li Genke , Liu Yu , Hua Yujie , Zhang Yixin , Zhou Guangdong
Published: June 2024

Cartilage tissue engineering is a promising strategy to repair damaged tissue and reconstruct organ function, but the scaffold‐free cartilage regeneration technology is currently limited in its ability to construct three‐dimensional (3D) shapes, maintain the chondrogenic phenotype, and express cartilage‐specific extracellular matrix (ECM). Recently, cartilaginous organoids (COs), multicellular aggregates with spheroid architecture, have shown great potential in miniaturized cartilage developmental models in vitro. However, high‐efficiency and transferable in vivo organoid‐based 3D cartilage regeneration technology for preclinical research needs further exploration. In this study, we develop novel cartilaginous organoids bioassembly (COBA) strategy to achieve scaffold‐free 3D cartilage regeneration, which displays batch‐to‐batch efficiency, structural integration, and functional reconstruction. For underlying molecule mechanism, cellular adhesion proteins significantly regulate cell aggregation and cytoskeleton reorganization to form cartilaginous spheroids, and the hypoxic microenvironment created by high‐density cell aggregates synergistically activates hypoxia‐inducible factor‐1α‐mediated glycolytic metabolism reprogramming to maintain the chondrogenic phenotype and promote cartilage‐specific ECM deposition. Furthermore, separated COs can integrate into a complete and continuous cartilage tissue through the COBA approach, and thus facilitate raising the nasal dorsa in goats after minimally invasive injection. This study thus demonstrates the promise of COBA technology to achieve scaffold‐free 3D cartilage regeneration for organoid‐based translational applications.
Optimized design of macro‐microreactor for scale‐up of liquid–liquid chemical processes
Authors: Zhao Shuangfei , Hu Xin , Wang Huiyue , Liu Yihuan , Fang Zheng , Guo Kai , Zhu Ning
Published: June 2024

The scale‐up of microreactor‐based flow chemical process represents a grand challenge in chemical engineering. The small characteristic size (<1000 μm) of a typical microreactor leads to not only microscale effect (process intensification) but also low throughput. Here, we report macro‐microreactor to achieve scale‐up of liquid–liquid chemical operation with process intensification. By incorporating the designed internals based on computational fluid dynamics, the characteristic size of the macro‐microreactor is expanded into 3000–4000 μm. The optimized design of macro‐microreactor with helical‐shaped internal exhibits both similar or even stronger microscale effect and high throughput in contrast to the typical microreactor. For the liquid–liquid chemical process, seven times higher mass transfer coefficient and about half reduction of the pressure drop are realized. These macro‐microreactors would find further applications in industrial chemical manufacturing.
Experimental and molecular insights on the regulatory effects of solvent on CaC2 reaction activity
Authors: Chen Zhengrun , Xu Hui , Zang Xiaoteng , Meng Hong , Fan Hongwei , Lu Yingzhou , Li Chunxi
Published: June 2024

Calcium carbide (CaC2) is a valuable carbanion resource, but the reactivity is highly restricted by its insolubility and super‐basicity. For this, the effect of solvent and mechanical forces on its reactivity is investigated extensively here via quantum chemistry calculation, molecular dynamic simulation, and experiments. The dissolution free energy of CaC2 in over 100 solvents has been evaluated. DMSO, CH3CN, and DMF can enhance the negative potential and reactivity of CaC2, especially DMSO. The electrostatic interaction of CaC2‐solvent mainly originates from the interaction between Ca2+ and O or N atom. The increased electron density around is mainly ascribed to the electron transfer from solvent. DMSO can change the ionic orientation of CaC2 interface. The solvent may be deprotonated by , compromising the solvent stability. The interface interaction of CaC2 with DMF and DMSO is verified through FT‐IR, and the lattice structure of CaC2 is lost virtually after 0.5 h mechanical milling.
Catalytic Aerobic Carbooxygenation for the Construction of Vicinal Tetrasubstituted Centers: Application to the Synthesis of Hexasubstituted γ‐Lactones
Authors: Pünner Florian , Sohtome Yoshihiro , Lyu Yanzong , Hashizume Daisuke , Akakabe Mai , Yoshimura Mami , Yashiroda Yoko , Yoshida Minoru , Sodeoka Mikiko
Published: June 2024

Strategic design for the construction of contiguous tetrasubstituted carbon centers represents a daunting challenge in synthetic organic chemistry. Herein, we report a combined experimental and computational investigation aimed at developing catalytic aerobic carbooxygenation, involving the intramolecular addition of tertiary radicals to geminally disubstituted alkenes, followed by aerobic oxygenation. This reaction provides a straightforward route to various α,α,β,β‐tetrasubstituted γ‐lactones, which can be readily transformed into hexasubstituted γ‐lactones through allylation/translactonization. Computational analysis reveals that the key mechanistic foundation for achieving the developed aerobic carbooxygenation involves the design of endothermic (energetically uphill) C−C bond formation followed by exothermic (energetically downhill) oxygenation. Furthermore, we highlight a unique fluorine‐induced stereoelectronic effect that stabilizes the endothermic stereodetermining transition state.
A Double Twisted Nanographene with a Contorted Pyrene Core
Authors: Dong Yanping , Zhang Zhiyu , Hashikawa Yoshifumi , Meng He , Bai Fenghua , Itami Kenichiro , Chaolumen
Published: June 2024

The mature synthetic methodologies enable us to rationally design and produce chiral nanographenes (NGs), most of which consist of multiple helical motifs. However, inherent chirality originating from twisted geometry has just emerged to be employed in chiral NGs. Herein, we report a red‐emissive chiral NG constituted of orthogonally arranged two‐fold twisted π‐skeletons at a contorted pyrene core which contributes to optical transitions of S0→S1 and vice versa. The thus‐obtained NG exhibited a robustness on its redox properties through 2e− uptake/release. The chemical oxidation generated stable radical cation whose absorption covers near‐infrared I and II regions. Overall, the contorted pyrene core governs electronic nature of the chiral NG. The twist operation on NGs would be, therefore, a design strategy to alter conventional chirality induction on NGs.
Closed‐Loop Recyclable Poly(ester‐disulfide)s for Potential Alternatives to Engineering Plastic
Authors: Chen Meng , Yang Rulin , Wu Huiping , Wang Qian , Shi Chenyu , Zhou Shang‐Wu , Yang Ding , Liu Fang‐Yu , Tian He , Qu Da‐Hui
Published: June 2024

Facile fabrication, low material complexity and closed‐loop recycling are essential for polymer plastics to alter their linear product economy towards a cradle‐to‐cradle one. Covalent adaptable networks (CANs) are one way to achieve that, which intrinsically exhibit decent mechanical properties like the thermosets but could also be easily recycled like the thermoplastics. In this work, we introduce rigid ester structural motifs into dynamic poly(disulfide)s to form a series of dual polymer networks. Owning to the coherence of soft/rigid segments and the reversible sacrificial crosslinking, they exhibit tailorable mechanical properties and good resistance towards different chemicals. Their closed‐loop recycling is achieved via mild solvolysis, maintaining materials’ mechanical integrities. It offers a solution as a sustainable replacement for engineering plastics which are massively under production but hard to be recycled.
Solvent Effects in Hyperpolarization of 15N Nuclei in [15N3]Metronidazole and [15N3]Nimorazole Antibiotics via SABRE‐SHEATH**
Authors: Yi Anna P. , Salnikov Oleg G. , Burueva Dudari B. , Chukanov Nikita V. , Chekmenev Eduard Y. , Koptyug Igor V.
Published: June 2024

Metronidazole and nimorazole are antibiotics of a nitroimidazole group which also may be potentially utilized as hypoxia radiosensitizers for the treatment of cancerous tumors. Hyperpolarization of 15N nuclei in these compounds using SABRE‐SHEATH (Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei) approach provides dramatic enhancement of detection sensitivity of these analytes using magnetic resonance spectroscopy and imaging. Methanol‐d4 is conventionally employed as a solvent in SABRE hyperpolarization process. Herein, we investigate SABRE‐SHEATH hyperpolarization of isotopically labeled [15N3]metronidazole and [15N3]nimorazole in nondeuterated methanol and ethanol solvents. Optimization of such hyperpolarization parameters as polarization transfer magnetic field, temperature, parahydrogen flow rate and pressure allowed us to obtain an average 15N polarization of up to 7.2–7.4 % for both substrates. The highest 15N polarizations were observed in methanol‐d4 for [15N3]metronidazole and in ethanol for [15N3]nimorazole. At a clinically relevant magnetic field of 1.4 T the 15N nuclei of these substrates possess long characteristic hyperpolarization lifetimes (T1) of ca. 1 to ca. 7 min. This study represents a major step toward SABRE in more biocompatible solvents, such as ethanol, and also paves the way for future utilization of these hyperpolarized nitroimidazoles as molecular contrast agents for MRI visualization of tumors.
Bringing genomics to the field: An integrative approach to seed sourcing for forest restoration
Authors: Prakash Anoob , Capblancq Thibaut , Shallows Kathryn , Saville David , Landau Deborah , Landress Chad , Jacobs Tal , Keller Stephen
Published: June 2024

Premise

Global anthropogenic change threatens the health and productivity of forest ecosystems. Assisted migration and reforestation are tools to help mitigate these impacts. However, questions remain about how to approach sourcing seeds to ensure high establishment and future adaptability.

Methods

Using exome‐capture sequencing, we demonstrate a computational approach to finding the best n‐sets from a candidate list of seed sources that collectively achieve high genetic diversity (GD) and minimal genetic load (GL), while also increasing evolvability in quantitative traits. The benefits of this three‐part strategy (diversity‐load‐evolvability) are to increase near‐term establishment success while also boosting evolutionary potential to respond to future stressors. Members of The Nature Conservancy and the Central Appalachian Spruce Restoration Initiative planted 58,000 seedlings across 255 acres. A subset of seedlings was monitored for establishment success and variation in growth.

Results

The results show gains in GD relative to GL and increases in quantitative genetic variation in seedling growth for pooled vs. single‐source restoration. No single “super source” was observed across planting sites; rather, monitoring results demonstrate that pooling of multiple sources helps achieve higher GD:GL and evolvability.

Discussion

Our study shows the potential for integrating genomics into local‐scale restoration and the importance of building partnerships between academic researchers and applied conservation managers.
Design, synthesis, and antiproliferative activity of new indole/1,2,4‐triazole/chalcone hybrids as EGFR and/or c‐MET inhibitors
Authors: Mahmoud Esraa , Abdelhamid Dalia , Youssif Bahaa G. M. , Gomaa Hesham A. M. , Hayallah Alaa M. , Abdel‐Aziz Mohamad
Published: June 2024

A novel group of indolyl‐1,2,4‐triazole‐chalcone hybrids was designed, synthesized, and assessed for their anticancer activity. The synthesized compounds exhibited significant antiproliferative activity. Compounds 9a and 9e exhibited significant cancer inhibition with GI50 ranging from 3.69 to 20.40 µM and from 0.29 to >100 µM, respectively. Both compounds displayed a broad spectrum of anticancer activity with selectivity ratios ranging between 0.50–2.78 and 0.25–2.81 at the GI50 level, respectively. The synthesized compounds were also screened for their cytotoxicity by 3‐(4,5‐dimethylthiazole‐2‐yl)‐2,5‐diphenyltetrazol (MTT) assay and for inhibition of epidermal growth factor receptor (EGFR) and c‐MET (mesenchymal‐epithelial transition factor). Some of the tested compounds exhibited significant inhibition against EGFR and/or c‐MET. Compound 9b showed the highest c‐MET inhibition (IC50 = 4.70 nM) compared to foretinib (IC50 = 2.5 nM). Compound 9d showed equipotent activity compared with erlotinib against EGFR (IC50 = 0.052 µM) and displayed significant c‐MET inhibition with an IC50 value of 4.90 nM.
Investigation of an Industrially Scalable Production of Sulfur‐Polyacrylonitrile Based Cathodes
Authors: Moschner Robin , Cavers Heather , Michalowski Peter , Kwade Arno
Published: June 2024

Sulfur‐polyacrylonitrile (SPAN) is a sulfur‐based active material for next‐generation lithium‐sulfur battery cathodes. Due to the covalent bonding between sulfur chains and the polymeric backbone, the shuttle effect degrading classical sulfur‐based cathodes can be suppressed while also achieving a high active material content in the cathode. In this paper, we investigate the processability of an industrially scalable SPAN active material with 38 wt.‐% of sulfur in a water‐based and scalable process route. The potential of the SPAN material for industrial adoption and the impact of the process route on the cell performance are discussed. We show that when processed correctly, the SPAN material delivers exceptional cycling stability and good C‐rate performance with ether‐based electrolytes. However, the performance of the SPAN cathode is influenced by the mixing characteristic. Using higher mixing intensities during the slurry preparation leads to deterioration of the electrochemical performance. This can be attributed to a decreasing carbon black percolation with increasing tip speed in combination with the kinetic limitation of sulfur cathodes during Li2S2 and Li2S oxidation.
Real‐world outcomes of patients with resected stage III melanoma treated with adjuvant therapies
Authors: Dima Danai , Lopetegui‐Lia Nerea , Ogbue Olisaemeka , Osantowski Bennett , Ullah Fauzia , Jia Xuefei , Song Jung Min , Gastman Brian , Isaacs James , Kennedy Lucy Boyce , Funchain Pauline
Published: June 2024

Background

Both immunotherapy (IO) and targeted therapy (TT) are used as adjuvant (adj) treatment for stage III melanoma, however, data describing real‐world outcomes are limited. In addition, a significant proportion of patients relapse, for whom best management is unclear. The aim of our study was to assess the efficacy, and safety of adj anti‐PD1 IO and TT in a real‐world cohort of patients with resected stage III melanoma, and further delineate patterns of recurrence and treatment strategies.

Methods

We retrospectively analyzed 130 patients who received adj therapy (100 anti‐PD1 IO and 30 TT).

Results

At a median follow‐up of 30 months, median relapse‐free survival (RFS) was 24.6 (95% CI, 17–not reached [NR]) versus 64 (95% CI, 29.5–NR) months for the TT and IO groups, respectively (p = 0.26). Median overall survival (OS) was NR for either subgroup. At data cutoff, 77% and 82% of patients in TT and IO arms were alive. A higher number of grade ≥3 treatment‐related adverse events (AEs) were noted in the IO group (11% vs. 3%), however, a higher proportion of patients permanently discontinued adj therapy in the TT group (43% vs. 11%) due to toxicity. Strategies at relapse and outcomes were variable based on location and timing of recurrence. A significant number of patients who relapsed after adj IO received a second round of IO. Among them, patients who were off adj IO at relapse had superior second median RFS (mRFS2), compared to those who relapsed while on adj IO; mRFS2 was NR versus 5.1 months (95% CI, 2.5–NR), respectively, p = 0.02.

Conclusion

In summary, both TT and IO yielded prolonged RFS in a real‐world setting, however, longer follow‐up is needed to determine any potential OS benefit. Adj therapy, particularly TT, may not be as well tolerated as suggested in clinical trials, with lower completion rates (59% vs. 74%) in a real‐life setting. Overall, patients who relapse during adj therapy have poor outcomes, while patients who relapse after discontinuation of adj IO therapy appear to benefit from IO re‐treatment.
Radiofrequency ablation in patients with obstructive hypertrophic cardiomyopathy: An updated comprehensive review and meta‐analysis
Authors: da Silva Menezes Antonio , Sanches Murilo R. , de Oliveira Filho Ernani , de Oliveira Elias J. R. , Oliveira Vinicius M. R. , Moraes Vitor R. Y.
Published: June 2024

Background

Radiofrequency catheter ablation (RFCA) has emerged as a therapeutic option for surgical myectomy and alcohol septal ablation (ASA) in patients with hypertrophic obstructive cardiomyopathy (HOCM), but its efficacy remains unclear.

Aim

Due to limited research on RFCA for HCM, there is an ongoing attempt to assess its efficacy and safety.

Methods

PubMed, Embase, and Scopus were systematically searched for studies assessing the efficacy outcomes for patients with HOCM who underwent RFCA. Mean differences (MDs) with 95% confidence intervals (CIs) were computed using a random‐effects model and heterogeneity was assessed using I2 statistics.

Results

We included 11 studies comprising 470 patients, of whom 34.6% were female. The mean patient age ranged from 43.7 to 60.7 years. During the follow‐up after RFCA, there was a significant decrease in the left ventricular outflow tract (LVOT) gradient at rest (MD −60.25 mmHg; 95% CI [−70.53;−59.14 mmHg]; p < 0.01) and during stimulation (MD −83.56 mmHg; 95% CI [−100.36;−66.76 mmHg]; p < 0.01). Moreover, RFCA reduced interventricular septum (IVS) thickness (MD −3.61 mm; 95% CI [−5.64; −1.59 mm]; p = 0.01) and New York Heart Association (NYHA) class (MD −1.46; 95% CI [−1.69; −1.24]; p < 0.01).

Conclusions

In patients with HOCM, RFCA was associated with an improved NYHA class, reduced IVS thickness, and decreased LVOT gradient at rest and with stimulation.
Long‐term outcomes after echocardiography versus fluoroscopy‐guided left atrial appendage closure: Is there still a role for a simplified approach?
Authors: Gilhofer Thomas S. , Schweiger Victor , Gehler Mario , Bokemeyer Victoria , Chen Mi , Candreva Alessandro , Würdinger Michael , Di Vece Davide , Templin Christian , Niederseer David , Stähli Barbara E. , Stehli Julia , Gotschy Alexander , Jakob Philipp , Ruschitzka Frank , Binder Ronald , Nietlispach Fabian , Michel Jonathan , Kasel A. Markus
Published: June 2024

Background

Left atrial appendage closure (LAAC) represents an alternative to oral anticoagulation for stroke prevention in patients with non‐valvular atrial fibrillation (AF). While transoesophageal echocardiography is the current standard for guiding LAAC procedures, several centers have employed fluoroscopic guidance alone. However, data on long‐term outcomes are lacking.

Methods

A total of 536 patients with AF undergoing LAAC and with available data on long‐term follow‐up were included in the retrospective, single‐center analysis. Outcomes of patients undergoing fluoroscopy‐guided LAAC were compared with those undergoing echocardiography guided LAAC. Time‐dependent analysis was performed with the Kaplan–Meier method.

Results

A total of 234 (44%) and 302 (56%) patients were treated with echocardiography and fluoroscopy guidance, respectively. Baseline characteristics did not differ between the two groups. Procedural success rates were high in both groups (97% of fluoroscopy vs. 98% of echocardiography guided procedures; p = 0.92) and rates of relevant peri‐device leaks (p = 0.50) and device‐related thrombus formation (p = 0.22) did not differ between groups. Median clinical follow‐up time was 48 (IQR 19–73) months. Rates of all‐cause mortality (p = 0.15, HR 0.83, CI 0.64–1.07) and stroke (p = 0.076, HR 2.23, CI 0.90–5.54) were comparable among groups.

Conclusion

LAAC with fluoroscopy guidance alone is equally safe and leads to similar clinical outcome compared to LAAC with additional echocardiography guidance.
1‐Haloalkynes: Privileged Substrates for Gold Catalysis
Authors: Miguélez Rubén , Arto Omar , Rodríguez‐Arias Carlos , González José Manuel , Barrio Pablo
Published: June 2024

Alkynes have been the preferred substrates since the early development of gold catalysis at the dawn of this century. Amongst them, 1‐haloalkynes have gained increased interest in recent years due to the versatility offered by these bifunctional entities as well as the identification of unique reaction modes in this already mature research field. Herein, the seminal contributions that resulted in the observed growth in recent years and the most recent developments will be discussed.
The ‘Open’ Site of Lewis Acid Zeolites for Meerwein‐Ponndorf‐Verley‐Oppenauer Reactions in Biomass Catalysis
Authors: Wu Meng , Liu Meng , Guo Pengfei , Lu Tianliang , Wu Zhijie , Luo Wenhao
Published: June 2024

Heteroatom zeolites are efficient catalysts for activating oxygenates in Meerwein‐Ponndorf‐Verley‐Oppenauer (MPVO) reactions, due to the unique Lewis acid character of their tetrahedral heteroatom metal sites. Such Lewis acid zeolites, especially heteroatom Beta zeolites, are intensively investigated with increasing attention in the valorization of biomass‐derived oxygenates. Herein, we first briefly review the recent development and advantage of Lewis acid zeolites for MPVO reactions involved in biomass valorization, majorly based on the selected case studies of the most representative heteroatom Beta zeolites. Increasing recognization of the open framework sites as the intrinsic active sites for Lewis acid zeolites in MPVO reactions has been discussed, with static and dynamic viewpoints. Furthermore, the recent progress on the development of characterization technologies applied in recent the state‐of‐the‐art showcases of identification and quantification of open sites, has been assessed, with a special focus on indirect detection using probe molecules and direct detection approaches. Future opportunities and challenges regarding the development of complimentary in situ characterization technologies and in‐depth understanding of the true nature of active sites and correlative mechanisms are examined for the ultimate goal of providing stable MPVO catalysts in biomass valorization.
Spatially Resolved Multicolor Luminescence Tuning on the Single 1D Heterogeneous Microrod
Authors: Lu Changyuan , You Wenwu
Published: June 2024

The spatially resolvable multicolored microrods have potential applications in many fields. However, achieving spatially resolved multicolor luminescence tuning on the microrod with a fixed composition remains a daunting challenge. Herein, a strategy is proposed that allows for the tuning of spatially resolved, multicolored upconversion (UC) luminescence (UCL) along a 1D heterogeneous microrod by modifying the pulse width of an external laser. NaYbF4:1 % Ho is identified as an UCL color‐adjustable material, exhibiting pulse width‐dependent multicolored UCL, resulting in a significant regulation of the red/green (R/G) ratio from 0.1 to 10.3 as the pulse width is varied from 0.1 to 10 ms. Such variability can be ascribed to differences in the number of photons incident upon the microrod throughout the period necessary for the UC process to occur. Additionally, NaYbF4:1 %Tm and NaYF4:20 %Yb,1 %Ho are employed as materials that emit blue and green light, respectively, with their UCL colors largely unaffected by changes in the pulse width. Subsequently, a tip‐modified epitaxial growth method is utilized to integrate both UCL color‐adjustable and non‐adjustable segments within the same microrod. Comparing with single‐color or fixed multicolor microrods, our developed multisegmented emissive color adjustable 1D heterogeneous microrods have unique optical characteristics and can carry more optical information.
Construction of Acyclic Quaternary Carbon Stereocenters via Enantioselective Nickel Catalysis†
Authors: Song Jian , Li Xuening , Long Jinguo , Yang Hua , Fang Xianjie
Published: June 2024

Comprehensive Summary

The construction of acyclic quaternary carbon stereocenters, which are ubiquitous in many bioactive compounds, pharmaceuticals and natural products, has been a long persuit in synthetic organic chemistry. Among numerous methods, enantioselective nickel‐catalysis has attracted incremental attention in recent years. This review summarizes the recent development in the asymmetric strategies, research progress, mechanistic investigations for the generation of acyclic quaternary carbon stereocenters via enantioselective nickel catalysis.

Key Scientists

In 2006, the Zhou group and RajanBabu group realized the nickel‐catalyzed enantioselective hydrovinylation of α‐substituted styrenes and ethylene to construct acyclic quaternary carbon stereocenters (QCSs) by using spiro‐ and binaphthyl phosphoramidite ligands, respectively. In 2016, Watson developed a nickel‐catalyzed Suzuki‐Miyaura arylation to generate acyclic QCSs via chirality transfer reaction. In 2017, the Feng and the Fu group developed nickel‐catalyzed enantioselective conjugated/Michael additions to build acyclic QCSs, respectively. In 2020, the Fang group made the first success in the construction of QCSs by nickel‐catalyzed hydrocyanation of alkenes and allenes. In 2021, Gregory C. Fu and co‐workers disclosed a nickel‐catalyzed enantioselective α‐functionalization of carbonyl compounds that could form acyclic QCSs. At the same time, the Shi group constructed chiral acyclic QCSs via nickel‐catalyzed functionalization of alkenes. In 2023, Kleij and co‐workers applied a new strategy for Ni‐catalyzed regio‐ and enantioselective homoallylic coupling to construct acyclic QCSs. In the same year, Tao and co‐workers demonstrated a novel strategy that is dinickel‐catalyzed enantioselective α‐alkylation of carbonyl compounds with alkyl iodides.
Regulating Built‐in Polar States via Atomic Self‐Hybridization for Fast Ion Diffusion Kinetics in Potassium Ion Batteries†
Authors: Du Hongwei , Zhou Xiaoyun , Li Tao , Zhao Wen , Zhou Dan , Yang Dawei , Wu Tianli , Xu Ying
Published: June 2024

Comprehensive Summary

Potassium ion batteries (PIBs) are of great interest owing to the low cost and abundance of potassium resources, while the sluggish diffusion kinetics of K+ in the electrode materials severely impede their practical applications. Here, self‐hybridized BiOCl0.5Br0.5 with a floral structure is assembled and used as anode for PIBs. Based on the systematic theoretical calculation and experimental analysis, the unbalance of charge distribution between Cl and Br atoms leads to an enhanced built‐in electric field and a larger interlayer spacing, which can enhance the K+ diffusion. Furthermore, the K+ insertion causes the energetic evolution of polar states in the BiOCl0.5Br0.5 crystal framework, where the dynamic correlation between the K+ and the halogen atoms leads to the formation of hole‐like polarons, which significantly improves the K+ diffusion and reaction kinetics during the charging/discharging process, giving important implications to design the electrode materials with high electrochemical performance by engineering the interaction between electronic structure and interface. Therefore, the BiOCl0.5Br0.5 anode obtains an excellent performance of 171 mAh·g–1 at 1 A·g–1 over 2000 cycles in PIBs.
Visible Light Catalyzed Reductive Cross‐Coupling of α‐CF3‐alkyl Bromide and Alkynyl Bromide†
Authors: Tian Yiqiang , Li Yi , Zhang Chun
Published: June 2024

Comprehensive Summary

Traditional reduction coupling reactions of two bromides typically rely on transition metal catalysis. Here, we introduce the development of a visible‐light catalytic direct reduction coupling reaction between α‐CF3‐alkyl bromides and alkynyl bromides to access valuable organic frameworks. Our research confirms the excellent compatibility of this reaction with various functional groups, which could be used to modify the substrate with biologically active molecular fragments. Mechanistic investigations, including control experiments, fluorescence quenching studies, and light‐switching experiments, have provided insights into the reaction mechanism. This study paves the way for the application of visible‐light catalysis in diverse synthetic transformations, offering a sustainable and efficient approach to organic synthesis.
Host‐Guest Chemistry and Nonlinear Optical Behaviors of Aluminum Molecular Rings†
Authors: Chen Yi‐Bo , Zhang Cheng‐Yang , Luo Dan , Chen Ran‐Qi , Zhang Jian , Chen Shu‐Mei , Fang Wei‐Hui
Published: June 2024

Comprehensive Summary

Macrocyclic compounds are of great interest for their ability to capture guest molecules into their cavities. In particular, host‐guest interaction plays a crucial role in the formation of supramolecular compounds. Herein, two host‐guest supramolecular compounds, [Al8(OH)8(L)16]·2HL (HL@AlOC‐166, HL = 4‐Iodobenzoic acid) and [Al8(OH)8(L)8(L1)8]·2DMF (DMF@AlOC‐166, HL1 = isoamyl alcohol), are acquired by introducing different types of guest components based on the internal pore cavities of the aluminum molecular ring [Al8(OH)8(L)16] (AlOC‐166). The inclusion of these guests is attributed to the presence of abundant hydrophilic OH serving as the hydrogen bond donors inward the ring cavity. Host‐guest compounds usually exhibit superior nonlinear optical (NLO) response due to the existence of guest molecules that could change symmetry, dipole moments, charge distributions, etc. Unexpectedly, the AlOC‐166 achieved the best NLO results, although it had no guest molecules inside its molecular ring, which breaks the traditional concept. The reason for this trend can be explained by the difference in intermolecular force rather than intramolecular interaction, mainly related to the amount and strength of π···π and C—I···π interactions in different compounds. This work investigates the effect of host‐guest interaction on NLO, representing a new perspective for designing optical limiting materials.
Lenvatinib plus pembrolizumab for patients with previously treated, advanced, triple‐negative breast cancer: Results from the triple‐negative breast cancer cohort of the phase 2 LEAP‐005 Study
Authors: Chung Hyun Cheol , Saada‐Bouzid Esma , Longo Federico , Yanez Eduardo , Im Seock‐Ah , Castanon Eduardo , Desautels Danielle N. , Graham Donna M. , Garcia‐Corbacho Javier , Lopez Juanita , Dutcus Corina , Okpara Chinyere E. , Ghori Razi , Jin Fan , Groisberg Roman , Korakis Iphigenie
Published: June 2024

Background

Novel treatments are needed for patients with advanced, triple‐negative breast cancer (TNBC) that progresses or recurs after first‐line treatment with chemotherapy. The authors report results from the TNBC cohort of the multicohort, open‐label, single‐arm, phase 2 LEAP‐005 study of lenvatinib plus pembrolizumab in patients with advanced solid tumors (ClinicalTrials.gov identifier NCT03797326).

Methods

Eligible patients had metastatic or unresectable TNBC with disease progression after one or two lines of therapy. Patients received lenvatinib (20 mg daily) plus pembrolizumab (200 mg every 3 weeks; up to 35 cycles). The primary end points were the objective response rate according to Response Evaluation Criteria in Solid Tumors, version 1.1, and safety (adverse events graded by the National Cancer Institute's Common Terminology Criteria for Adverse Events, version 4.0). Duration of response, progression‐free survival, and overall survival were secondary end points.

Results

Thirty‐one patients were enrolled. The objective response rate by investigator assessment was 23% (95% confidence interval [CI], 10%–41%). Overall, the objective response rate by blinded independent central review (BICR) was 32% (95% CI, 17%–51%); and, in patients who had programmed cell death ligand 1 combined positive scores ≥10 (n = 8) and <10 (n = 22), the objective response rate was 50% (95% CI, 16%–84%) and 27% (95% CI, 11%–50%), respectively. The median duration of response by BICR was 12.1 months (range, from 3.0+ to 37.9+ months). The median progression‐free survival by BICR was 5.1 months (95% CI, 1.9–11.8 months) and the median overall survival was 11.4 months (95% CI, 4.1–21.7 months). Treatment‐related adverse events occurred in 94% of patients (grade 3, 52%; grade 4, 0%). One patient died due to a treatment‐related adverse event of subarachnoid hemorrhage.

Conclusions

The combination of lenvatinib plus pembrolizumab demonstrated antitumor activity with a manageable safety profile in patients with previously treated, advanced TNBC.
Top advances of the year: Targeted therapy for lung cancer
Authors: Makarem Maisam , Jänne Pasi A.
Published: June 2024

The past year has offered significant advancements in the field of non–small cell lung cancer (NSCLC), both in the early and advanced disease settings. The identification of guideline‐recommended actionable targets has provided the foundation for developing multiple new therapeutic agents. There has been a focus on developing drugs designed to overcome acquired resistance, a limitation of tyrosine kinase inhibitor–based therapy in lung cancer. In addition, there is an emerging trend toward combination therapies for patients in the first‐line setting with the goal of preventing or delaying resistance. Another promising area of development has been the use of antibody–drug conjugates, where there are the initial reports of central nervous system efficacy and activity in patients with genomic alterations. Over the past year, numerous publications and presentations have highlighted multiple therapeutic advances, offering new treatment options for patients with NSCLC. The focus of this review is to summarize the most impactful findings, emphasizing their significance in the evolving treatment landscape for NSCLC. Several landmark trials in lung cancer with practice‐changing clinical implications have been presented and published in 2023. This article reviews a selection of these trials as they relate to early and advanced‐stage oncogene‐driven lung cancer. The ADAURA and ALINA trials, in which targeted therapy given in the adjuvant setting has demonstrated improved clinical outcomes, are reviewed. In the advanced‐stage setting, recent trials in the context of specific oncogene drivers are reviewed, including EGFR, ALK, ROS1, RET, ERBB2 (HER2), BRAF, MET exon 14 skipping (METex14), and KRAS alterations. Also discussed are the results of several trials that have evaluated the use of combination therapies and resistance‐mechanism agnostic treatment strategies.

Plain Language Summary

Targeted therapy plays an important role for patients with early and advanced‐stage non–small cell lung cancer carrying specific genetic alterations.

New strategies that combine multiple therapies are now being studied in randomized clinical trials, with the goal of enhancing the effectiveness of targeted therapy for patients with advanced lung cancer.
Asking the right questions surrounding opioid prescribing in cancer survivorship: Might all pain be cancer‐related?
Authors: Goodlev Eric R.
Published: June 2024

Current guidance surrounding pain management in cancer survivorship relies heavily on clinicians’ judgement of the pain’s cancer‐relatedness. Rather than asking whether the pain is cancer‐related, instead seek to understand the biopsychosocial and existential context of the pain, and ask whether the benefits of opioid therapy outweigh the risks.