bluuebunny/crossref_metadata_2025_split huggingface dataset:
Understanding the Cathode‐Electrolyte Interfacial Chemistry in Rechargeable Magnesium Batteries
Authors: Shi Hucheng , Wang Guixin , Wang Zhechen , Yang Lin , Zhang Shu , Dong Shanmu , Qu Baihua , Du Aobing , Li Zhenyou , Zhou Xiaoyuan , Cui Guanglei 
Published: April 2024

AbstractRechargeable magnesium batteries (RMBs) have garnered significant attention due to their potential to provide high energy density, utilize earth‐abundant raw materials, and employ metal anode safely. Currently, the lack of applicable cathode materials has become one of the bottleneck issues for fully exploiting the technological advantages of RMBs. Recent studies on Mg cathodes reveal divergent storage performance depending on the electrolyte formulation, posing interfacial issues as a previously overlooked challenge. This minireview begins with an introduction of representative cathode‐electrolyte interfacial phenomena in RMBs, elaborating on the unique solvation behavior of Mg2+, which lays the foundation for interfacial chemistries. It is followed by presenting recently developed strategies targeting the promotion of Mg2+ desolvation in the electrolyte and alternative cointercalation approaches to circumvent the desolvation step. In addition, efforts to enhance the cathode‐electrolyte compatibility via electrolyte development and interfacial engineering are highlighted. Based on the abovementioned discussions, this minireview finally puts forward perspectives and challenges on the establishment of a stable interface and fast interfacial chemistry for RMBs.
Designing Complex Tapestries with Photography‐Inspired Manipulation of Self‐Organized Thin‐Films
Authors: van Campenhout C. T. , Bistervels M. H. , Rietveld J. , Schoenmaker H. , Kamp M. , Noorduin W. L. 
Published: April 2024

AbstractThin‐films patterned with complex motifs are of fundamental interest because of their advanced optical, mechanical and electronic properties, but fabrication of these materials remains challenging. Self‐organization strategies, such as immersion controlled reaction‐diffusion patterning, have shown great potential for production of patterned thin‐films. However, the autonomous nature of such processes limits controllable pattern customizability and complexity. Here, it is demonstrated that photography inspired manipulation processes can overcome this limitation to create highly‐complex tapestries of micropatterned films (MPF's). Inspired by classical photographic processes, MPF's are developed, bleached, exposed, fixed, and contoured into user‐defined shapes and photographic toning reactions are used to convert the chemical composition MPF's, while preserving the original stripe patterns. By applying principles of composite photography, highly complex tapestries composed of multiple MPF layers are designed, where each layer can be individually manipulated into a specific shape and composition. By overcoming fundamental limitations, this synergistic approach broadens the design possibilities of reaction‐diffusion processes, furthering the potential of self‐organization strategies for the development of complex materials.
Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia
Authors: He Xinjia , Wen Yingke , Fang Yanjie , Li Mengjie , Shan Bing 
Published: April 2024

AbstractIn the design of photoelectrocatalytic cells, a key element is effective photogeneration of electron‐hole pairs to drive redox activation of catalysts. Despite recent progress in photoelectrocatalysis, experimental realization of a high‐performance photocathode for multi‐electron reduction of chemicals, such as nitrate reduction to ammonia, has remained a challenge due to difficulty in obtaining efficient electrode configurations for extraction of high‐throughput electrons from absorbed photons. This work describes a new design for catalytic photoelectrodes using chromophore assembly‐functionalized covalent networks for boosting eight‐electron reduction of nitrate to ammonia. Upon sunlight irradiation, the photoelectrode stores a mass of reducing equivalents at the photoexcited chromophore assembly for multielectron reduction of a copper catalyst, enabling efficient nitrate reduction to ammonia. By introducing the new photoelectrode structure, it is demonstrated that the electronic interplay between charge photo‐accumulating assembly and multi‐electron redox catalysts can be optimized to achieve proper balance between electron transfer dynamics and thermodynamic output of photoelectrocatalytic systems.
Radical‐Mediated Degradation of Thiol–Maleimide Hydrogels
Authors: Hebner Tayler S. , Kirkpatrick Bruce E. , Fairbanks Benjamin D. , Bowman Christopher N. , Anseth Kristi S. , Benoit Danielle S.W. 
Published: April 2024

AbstractMichael addition between thiol‐ and maleimide‐functionalized molecules is a long‐standing approach used for bioconjugation, hydrogel crosslinking, and the functionalization of other advanced materials. While the simplicity of this chemistry enables facile synthesis of hydrogels, network degradation is also desirable in many instances. Here, the susceptibility of thiol–maleimide bonds to radical‐mediated degradation is reported. Irreversible degradation in crosslinked materials is demonstrated using photoinitiated and chemically initiated radicals in hydrogels and linear polymers. The extent of degradation is shown to be dependent on initiator concentration. Using a model linear polymer system, the radical‐mediated mechanism of degradation is elucidated, in which the thiosuccinimide crosslink is converted to a succinimide and a new thioether formed with an initiator fragment. Using laser stereolithography, high‐fidelity spatiotemporal control over degradation in crosslinked gels is demonstrated. Ultimately, this work establishes a platform for controllable, radical‐mediated degradation in thiol–maleimide hydrogels, further expanding their versatility as functional materials.
Carrier‐Free Self‐Assembly Nano‐Sonosensitizers for Sonodynamic‐Amplified Cuproptosis‐Ferroptosis in Glioblastoma Therapy
Authors: Zhu Yang , Niu Xuegang , Ding Chengyu , Lin Yuanxiang , Fang Wenhua , Yan Lingjun , Cheng Junjie , Zou Jianhua , Tian Yu , Huang Wei , Huang Wen , Pan Yuanbo , Wu Tiantian , Chen Xiaoyuan , Kang Dezhi 
Published: April 2024

AbstractCuproptosis is a newly discovered form of programmed cell death significantly depending on the transport efficacy of copper (Cu) ionophores. However, existing Cu ionophores, primarily small molecules with a short blood half‐life, face challenges in transporting enough amounts of Cu ions into tumor cells. This work describes the construction of carrier‐free nanoparticles (Ce6@Cu NPs), which self‐assembled by the coordination of Cu2+ with the sonosensitizer chlorin e6 (Ce6), facilitating sonodynamic‐triggered combination of cuproptosis and ferroptosis. Ce6@Cu NPs internalized by U87MG cells induce a sonodynamic effect and glutathione (GSH) depletion capability, promoting lipid peroxidation and eventually inducing ferroptosis. Furthermore, Cu+ concentration in tumor cells significantly increases as Cu2+ reacts with reductive GSH, resulting in the downregulation of ferredoxin‐1 and lipoyl synthase. This induces the oligomerization of lipoylated dihydrolipoamide S‐acetyltransferase, causing proteotoxic stress and irreversible cuproptosis. Ce6@Cu NPs possess a satisfactory ability to penetrate the blood‐brain barrier, resulting in significant accumulation in orthotopic U87MG‐Luc glioblastoma. The sonodynamic‐triggered combination of ferroptosis and cuproptosis in the tumor by Ce6@Cu NPs is evidenced both in vitro and in vivo with minimal side effects. This work represents a promising tumor therapeutic strategy combining ferroptosis and cuproptosis, potentially inspiring further research in developing logical and effective cancer therapies based on cuproptosis.
Hypervalent Iodine Mediated Synthesis of 2‐Aminobenzazoles and 2‐Aminobenzothiazoles
Authors: Gu Yi , Li Yao‐Dong , Ge Ye , Huang Jiang‐Long , Xu Hua‐Jin , Hu Yi 
Published: April 2024

AbstractThe hypervalent iodine mediated, silica gel promoted synthesis of 2‐aminobenzazoles and 2‐aminobenzothiazole derivatives under metal‐free mild conditions within short time (30 min) has been developed. Under this process, PhI(COOCF3)2 (PIFA) or PhI(COOCH3)2 (PIDA) acts as an oxidant and radical initiator direct activated the ortho‐C−H bond of substrate, silica gel as weakly lewis acid effectively increased the reactivity of the reaction system. This method is compatible with various of arylurea and arylthiourea substrates, which is green, efficient, simple to operate and suitable for practical application.
The Trotter collection: A review of Mildred Trotter's hair research and an update for studies of human variation
Authors: Koch Sandra L. , Zaidi Arslan , González Tomás , Shriver Mark D. , Jablonski Nina G. 
Published: April 2024

AbstractObjectivesMildred Trotter was an anatomist and physical anthropologist whose studies on hair morphology, growth, somatic distribution, and trait relationships to age and ethnogeographic population were foundational to the field of microscopical hair analysis. The collection of human hair samples she assembled for her research has been an underutilized resource for studies on human hair variation. We applied updated methods and reviewed Trotter's original data to reassess the relationship hair traits have to diverse population labels.MethodsHair form and pigmentation patterns were measured from a subset of the hair samples accumulated by Trotter and we compared our data to Trotter's original results. Variability in hair traits were tested within individuals, within populations, and among ethnogeographic groups.ResultsMeasured hair cross‐section dimensions and melanosome density and distribution revealed substantial variability within individuals and ethnogeographic populations. Hair traits were found to not be distinctly separable by ancestry but instead showed continuous variation across human populations. Trotter's measurements were precise and the dataset she compiled remains valid, though the conclusions should be reviewed in light of our current understanding of human variation.DiscussionOur findings support moving away from categorical ancestry classifications and eliminating the use of outdated racial typologies in favor of more descriptive trait analysis. Detailed analysis of trait pattern distributions are presented that may be useful for future research on human variation. We point to the need for additional research on human variation and hair trait relationships with reference to known population affinity.
Elucidation of Palmarumycin Spirobisnaphthalene Biosynthesis Reveals a Set of Previously Unrecognized Oxidases and Reductases
Authors: Zhao Siji , Shen Zhen , Zhai Ziqi , Yin Ruya , Xu Dan , Wang Mingan , Wang Qi , Peng You‐Liang , Zhou Ligang , Lai Daowan 
Published: April 2024

AbstractSpirobisnaphthalenes (SBNs) are a class of highly oxygenated, fungal bisnaphthalenes containing a unique spiroketal bridge, that displayed diverse bioactivities. Among the reported SBNs, palmarumycins are the major type, which are precursors for the other type of SBNs structurally. However, the biosynthesis of SBNs is unclear. In this study, we elucidated the biosynthesis of palmarumycins, using gene disruption, heterologous expression, and substrate feeding experiments. The biosynthetic gene cluster for palmarumycins was identified to be distant from the polyketide synthase gene cluster, and included two cytochrome P450s (PalA and PalB), and one short chain dehydrogenase/reductase (PalC) encoding genes as key structural genes. PalA is an unusual, multifunctional P450 that catalyzes the oxidative dimerization of 1,8‐dihydroxynaphthalene to generate the spiroketal linkage and 2,3‐epoxy group. Chemical synthesis of key intermediate and in vitro biochemical assays proved that the oxidative dimerization proceeded via a binaphthyl ether. PalB installs the C‐5 hydroxy group, widely found in SBNs. PalC catalyzes 1‐keto reduction, the reverse 1‐dehydrogenation, and 2,3‐epoxide reduction. Moreover, an FAD‐dependent oxidoreductase, encoded by palD, which locates outside the cluster, functions as a 1‐dehydrogenase. These results provided the first genetic and biochemical evidence for the biosynthesis of palmarumycin SBNs.
Chemical Synthesis of Acetobacter pasteurianus Lipid A with a Unique Tetrasaccharide Backbone and Evaluation of Its Immunological Functions
Authors: Yamaura Haruki , Shimoyama Atsushi , Hosomi Koji , Kabayama Kazuya , Kunisawa Jun , Fukase Koichi 
Published: April 2024

AbstractLipopolysaccharide (LPS), a cell surface component of Gram‐negative bacteria, activates innate immunity. Its active principle is the terminal glycolipid lipid A. Acetobacter pasteurianus is a Gram‐negative bacterium used in the fermentation of traditional Japanese black rice vinegar (kurozu). In this study, we focused on A. pasteurianus lipid A, which is a potential immunostimulatory component of kurozu. The active principle structure of A. pasteurianus lipid A has not yet been identified. Herein, we first systematically synthesized three types of A. pasteurianus lipid As containing a common and unique tetrasaccharide backbone. We developed an efficient method for constructing the 2‐trehalosamine skeleton utilizing borinic acid‐catalyzed glycosylation to afford 1,1’‐α,α‐glycoside in high yield and stereoselectivity. A common tetrasaccharide intermediate with an orthogonal protecting group pattern was constructed via [2+2] glycosylation. After introducing various fatty acids, all protecting groups were removed to achieve the first chemical synthesis of three distinct types of A. pasteurianus lipid As. After evaluating their immunological function using both human and murine cell lines, we identified the active principles of A. pasteurianus LPS. We also found the unique anomeric structure of A. pasteurianus lipid A contributes to its high chemical stability.
One‐Step Butadiene Purification in a Sulfonate‐Functionalized Metal–Organic Framework through Synergistic Separation Mechanism
Authors: Cui Jiyu , Qiu Zhensong , Yang Zhenglu , Jin Anye , Cui Xili , Yang Lifeng , Xing Huabin 
Published: April 2024

AbstractPorous materials that could recognize specific molecules from complex mixtures are of great potential in improving the current energy‐intensive multistep separation processes. However, due to the highly similar structures and properties of the mixtures, the design of desired porous materials remains challenging. Herein, a sulfonate‐functionalized metal–organic framework ZU‐609 with suitable pore size and pore chemistry is designed for 1,3‐butadiene (C4H6) purification from complex C4 mixtures. The sulfonate anions decorated in the channel achieve selective recognition of C4H6 from other C4 olefins with subtle polarity differences through C−H⋅⋅⋅O−S interactions, affording recorded C4H6/trans‐2‐C4H8 selectivity (4.4). Meanwhile, the shrunken mouth of the channel with a suitable pore size (4.6 Å) exhibits exclusion effect to the larger molecules cis‐2‐C4H8, iso‐C4H8, n‐C4H10 and iso‐C4H10. Benefiting from the moderate C4 olefins binding affinity exhibited by sulfonate anions, the adsorbed C4H6 could be easily regenerated near ambient conditions. Polymer‐grade 1,3‐butadiene (99.5 %) is firstly obtained from 7‐component C4 mixtures via one adsorption‐desorption cycle. The work demonstrates the great potential of synergistic recognition of size‐sieving and thermodynamically equilibrium in dealing with complex mixtures.
Temperature‐Controlled Selective Formation of Silver Nanoclusters and Their Transformation to the Same Product
Authors: Wang Zhi , Wang Yuchen , Xu Tian‐Yang , Li Li , Aikens Christine M. , Gao Zhi‐Yong , Azam Mohammad , Tung Chen‐Ho , Sun Di 
Published: April 2024

AbstractHerein, two atomically precise silver nanoclusters, Ag54 and Ag33, directed by inner anion templates (CrO42− and/or Cl−), are initially isolated as a mixed phase from identical reactants across a wide temperature range (20–80 °C). Interestingly, fine‐tuning the reaction temperature can realize pure phase synthesis of the two nanoclusters; that is, a metastable Ag54 is kinetically formed at a low temperature (20 °C), whereas such a system is steered towards a thermodynamically stable Ag33 at a relatively high temperature (80 °C). Electrospray ionization mass spectrometry illustrates that the stability of Ag33 is superior to that of Ag54, which is further supported by density functional theory calculations. Importantly, the difference in structural stability can influence the pathway of 1,4‐bis(pyrid‐4‐yl)benzene induced transformation reaction starting from Ag54 and Ag33. The former undergoes a dramatic breakage‐reorganization process to form an Ag31 dimer (Ag31), while the same product can be also achieved from the latter following a noninvasive ligand exchange process. Both the Ag54 and Ag33 have the potential for further remote laser ignition applications. This work not only demonstrates how temperature controls the isolation of a specific phase, but also sheds light on the structural transformation pathway of nanoclusters with different stability.
Covalent Organic Framework Interlayer Spacings as Perfectly Selective Artificial Proton Channels
Authors: Li Qi , Gao Hongfei , Zhao Yongye , Zhou Bo , Yu Lei , Huang Qingsong , Jiang Lei , Gao Jun 
Published: April 2024

AbstractBiological proton channels have perfect selectivity in aqueous environment against almost all ions and molecules, a property that differs itself from other biological channels and a feature that remains challenging to realize for bulk artificial materials. The biological perfect selectivity originates from the fact that the channel has almost no free space for ion or water transport but generates a hydrogen bonded wire in the presence of protons to allow the proton hopping. Inspired by this, we used the interlayer spacings of covalent organic framework materials consisting of hydrophilic functional groups as perfectly selective artificial proton channels. The interlayer spacings are so narrow that no atoms or molecules can diffuse through. However, protons exhibit a diffusivity in the same order of magnitude as that in bulk water. Density functional theory calculations show that water molecules and the COF material form hydrogen bonded wires, allowing the proton hopping. We further demonstrate that the proton transport rate can be tuned by adjusting the acidity of the functional groups.
Tandem Catalysts Enabling Efficient C−N Coupling toward the Electrosynthesis of Urea
Authors: Gao Yuhang , Wang Jingnan , Sun Menglong , Jing Yuan , Chen Lili , Liang Zhiqin , Yang Yijun , Zhang Chuang , Yao Jiannian , Wang Xi 
Published: April 2024

AbstractThe development of a methodology for synthesizing value‐added urea (CO(NH2)2) via a renewable electricity‐driven C−N coupling reaction under mild conditions is highly anticipated. However, the complex catalytic active sites that act on the carbon and nitrogen species make the reaction mechanism unclear, resulting in a low efficiency of C−N coupling from the co‐reduction of carbon dioxide (CO2) and nitrate (NO3−). Herein, we propose a novel tandem catalyst of Mo‐PCN‐222(Co), in which the Mo sites serve to facilitate nitrate reduction to the *NH2 intermediate, while the Co sites enhance CO2 reduction to carbonic oxide (CO), thus synergistically promoting C−N coupling. The synthesized Mo‐PCN‐222(Co) catalyst exhibited a noteworthy urea yield rate of 844.11 mg h−1 g−1, alongside a corresponding Faradaic efficiency of 33.90 % at −0.4 V vs. reversible hydrogen electrode (RHE). By combining in situ spectroscopic techniques with density functional theory calculations, we demonstrate that efficient C−N coupling is attributed to a tandem system in which the *NH2 and *CO intermediates produced by the Mo and Co active sites of Mo‐PCN‐222(Co) stabilize the formation of the *CONH2 intermediate. This study provides an effective avenue for the design and synthesis of tandem catalysts for electrocatalytic urea synthesis.
Semi‐aromatic polyamide containing ether bond/hydroxyapatite composites: Preparation, structure and cytocompatibility
Authors: Chen Chaobi , Lyu Defu , Xi Wenjing , Chen Lichao , Cai Shijie , Yan Yonggang , Li Xiaodan , Ren Haohao , Xing Rong 
Published: April 2024

AbstractIn this work, semi‐aromatic polyamide containing ether bond (PAE10T) was synthesized through nucleophilic substitution reaction using 1, 10‐N, N′‐bis(4‐fuorobenzamide) decane (BFBD) and hydroquinone (HQ) as the raw materials. And then the composites hydroxyapatite/semi‐aromatic polyamide (40%HA‐PAE10T and 60%HA‐PAE10T) were prepared by chemical precipitation method. Mechanical, SEM, FT‐IR, XRD, DSC, TGA and bioactivity tests were performed to characterize the structure, morphology, thermal and mechanical properties of PAE10T and its composites. Mechanical tests revealed that the difference of HA in weight played an important role in mechanical performance of the composites. Furthermore, in comparison with PAE10T, the 60%HA‐PAE10T showed the highest enhancement in compressive strength (133 MPa) at 75.9%, and the 40%HA‐PAE10T given expression to the best increase in bending strengths (97 MPa) at about 18.4%. The 40%HA‐PAE10T and 60% HA‐PAE10T exhibited the mechanical performances closed to the cortical bone of human. After 28 days of dip in the phosphate buffer saline (PBS), PAE10T, and its composites showed satisfactory stability. The cell culture results showed all composites gad good cytocompatibility, cells attached on the materials well with excellent morphology. All the experimental results showed that the composites were expected to have a good application in the field of compact bone repair.
Effects of blending poly (polyol sebacate) and poly (polyol adipate) bioelastomers for soft tissue engineering in biomedical applications
Authors: Norouznezhad Afshin , Mir Mohamad Sadeghi Gity 
Published: April 2024

AbstractIn this article, the synthesis of four novel bioelastomers known as poly (xylitol sebacate) (PXS), poly (xylitol adipate) (PXA), poly (sorbitol sebacate) (PSS), and poly (sorbitol adipate) (PSA) was carried out through bulk polymerization, followed by their blending using the solution method. Six blends were prepared namely PXS25/PSS75, PXS50/PSS50, PXS75/PSS25, PXS50/PXA50, PSA50/PXA50, and PSS50/PSA50. After blending, a thermal curing process was applied to the samples. The intrinsic viscosity, density, Tg, hydrophilicity, degradation, wound healing, and mechanical properties of polymers and blends were measured to investigate the effects of blending. Analyzing hardness, modulus, stress at breakpoint, degradation, and hydrophilicity data showed that the mechanical properties of bioelastomers are adjustable by blending for tissue engineering. Furthermore, the scratch assay proved the biocompatibility of pure polymers and indicated that blending does not have a negative impact on this matter.