bluuebunny/crossref_metadata_2025 huggingface dataset:
Molecular Probe Embedded Porous Polymer Scaffold as Solid‐State Visual Sensor for Selective and Sequential Sensing of Ultra‐Trace Toxic Heavy Metal Ions in Environmental/Commercial Samples
Authors: Sivaraman Sushmitha P , Srinivasan Prabhakaran , Madhu Deepan Kumar , Chinaraga Pitchaiah K , Rao Brahmmananda C V S , Nagarajan Sivaraman , Deivasigamani Prabhakaran , Mohan Akhila Maheswari
Published: December 2023

The article reports on the tailor‐made solid‐state optical sensor through controlled imbuement of an amphiphilic probe onto a dual interwoven macro‐/meso‐porous polymer monolithic scaffold for the selective ocular sensing of ultra‐trace toxic heavy metal ions. The structural/surface morphology of the poly(LMC‐co‐TMP) monolith is customized through the stochiometric inclusion of lauryl methacrylate (LMC), trimethyl propanetrimethacrylate (TMP) and porogenic solvents. The riveting sensing performance of the poly(LMC‐co‐TMP) scaffolds for the target ions arises from the built‐in twofold intermingled porous architects that render voluminous surface area and porosity for the embedding of 2‐((1H‐benzoimidazol‐2‐yl)‐4‐butan‐2‐yl)phenol (HBBP), a chromoionophoric probe. The sensor's unique structural and surface properties endure stable ion‐complexation through color transitions from yellow (blank) to a leafy green, peanut brown, and dark blue for Pb2+, Hg2+, and Cd2+, respectively. The sensor imposes high binding affinity for the target ions, with a linear response range of 0–200 ppb for Pb2+/Hg2+ and 0–300 ppb for Cd2+. The detection limit values are 0.46, 0.52, and 0.41 ppb for Pb2+, Hg2+, and Cd2+, respectively. The sensor's hassle‐free on‐field testing in environmental and synthetic samples reveals excellent data reproducibility (Relative Standard Deviation (RSD) ≤1.97%), with pH‐assisted reliable color transitions for eight regenerative trials, with a response time of 45 s.
Large Tolerance of Lasing Properties to Impurity Defects in GaAs(Sb)‐AlGaAs Core‐Shell Nanowire Lasers
Authors: Schreitmüller Tobias , Jeong Hyowon W. , Esmaielpour Hamidreza , Mead Christopher E. , Ramsteiner Manfred , Schmiedeke Paul , Thurn Andreas , Ajay Akhil , Matich Sonja , Döblinger Markus , Lauhon Lincoln J. , Finley Jonathan J. , Koblmüller Gregor
Published: December 2023

GaAs‐AlGaAs based nanowire (NW) lasers hold great potential for on‐chip photonic applications, where lasing metrics have steadily improved over the years by optimizing resonator design and surface passivation methods. The factor that will ultimately limit the performance will depend on material properties, such as native‐ or impurity‐induced point defects and their impact on non‐radiative recombination. Here, the role of impurity‐induced point defects on the lasing performance of low‐threshold GaAs(Sb)‐AlGaAs NW‐lasers is evaluated, particularly by exploring Si‐dopants and their associated vacancy complexes. Si‐induced point defects and their self‐compensating nature are identified using correlated atom probe tomography, resonant Raman scattering, and photoluminescence experiments. Under pulsed optical excitation the lasing threshold is remarkably low (<10 µJ cm−2) and insensitive to impurity defects over a wide range of Si doping densities, while excess doping ([Si]>1019 cm−3) imposes increased threshold at low temperature. These characteristics coincide with increased Shockley‐Read‐Hall recombination, reflected by shorter carrier lifetimes, and reduced internal quantum efficiencies (IQE) . Remarkably, despite the lower IQE the presence of self‐compensating Si‐vacancy defects provides an improved temperature stability in lasing threshold with higher characteristic temperature and room‐temperature lasing. These findings highlight an overall large tolerance of lasing metrics to impurity defects in GaAs‐AlGaAs based NW‐lasers.
A Lithium‐Salt‐Free, Hydrophobic, Solid‐State Poly(Ionic Liquid) Electrolyte Enables Rapid Assembly of Unencapsulated, Removable Electrochromic “Window Tint Film”
Authors: Wu Xilu , Bai Zhiyuan , Bao Bingwei , Zhang Qinghong , Jiang Weizhong , Li Yaogang , Hou Chengyi , Li Kerui , Wang Hongzhi
Published: December 2023

Electrochromic technology that enables modulation of a material's optical properties by application of an applied voltage is utilized in smart windows. However, avoiding water absorption by lithium salt in the electrolyte necessitates complex encapsulated device assemblies that must be constructed under strict atmosphere conditions and are largely unrepairable. Herein, a lithium‐salt‐free, hydrophobic, solid‐state poly(ionic liquid) electrolyte based on strong C─F bonds that exhibits low polarizability, low moisture absorption, and a wide electrochemical window, allowing the fabrication of unencapsulated electrochromic devices with outstanding long‐term cycling and environmental stability are presented. Intimate contact between the electrolyte and the electrode is achieved through integrated in situ polymerization, providing an interface with multiple molecular interactions that impart robust adhesion, efficient ion transport, and excellent stability. To demonstrate the potential of this electrolyte for cost‐effective electrochromic smart windows, low‐cost (≈110 USD m−2), unencapsulated, removable, electrochromic “window tint film” with customizable dimensions and shapes are fabricated.
Divalent Viologen Cation‐Based Ionogels Facilitate Reversible Intercalation of Anions in PProDOT‐Me2 for Flexible Electrochromic Displays
Authors: Bai Zhiyuan , Wu Xilu , Fang Rui , Lu Ziqiu , Hou Chengyi , Zhang Qinghong , Li Yaogang , Li Kerui , Wang Hongzhi
Published: December 2023

The electrochromic (EC) polymer poly (3,4‐(2,2‐dimethylpropylenedioxy)thiophene) (PProDOT‐Me2) is expected to be used in flexible e‐paper displays because of its great optical modulation ability and inherent flexibility. While the EC effect is primarily determined by the anions and cations in the electrolyte, yet suffers from inorganic salt based on monovalent Li+ cations and corresponding anions, such as lithium perchlorate(LiClO4), lithium bis(trifluoromethane sulfonyl) imide (LiTFSI), and lithium trifluoromethane sulfonate (LiTRIF), which may impact the overall EC performance of the EC device caused by insufficient ion doping/de‐doping processes. Herein, the divalent viologen cation‐based ionogel (VGE) is developed to tackle the challenge. Owing to its more anions design, the doping/de‐doping process in the PProDOT‐Me2 is more sufficient, thereby enhancing the optical modulation range (ΔR = 39.4%) of PProDOT‐Me2, compared to monovalent Li+ cation‐based ionogel (ΔR = 13.3%). Meanwhile, the VGE has good interface contact with PProDOT‐Me2 and the flexible electrode, which makes the VGE‐based EC device (V‐ECD) exhibit commendable mechanical stability. To demonstrate the potential application in flexible e‐paper displays, the simple eight‐digit EC display device is assembled from seven V‐ECDs, each of which hasa high switching speed, robust cycling stability, and low operating energy consumption.
Chemically Tailored Single Atoms for Targeted and Light‐Controlled Bactericidal Activity
Authors: Li Zaoming , Zhao Zhiqiang , Chen Shutong , Wu Wenjie , Jin Ying , Mao Junjie , Lin Yuqing , Jiang Ying
Published: December 2023

Single‐atom (SA) nanoparticles exhibit considerable potential in terms of photothermal properties for bactericidal applications. Nevertheless, the restricted efficacy of their targeted and controlled antibacterial activity has hindered their practical implementation. This study aims to overcome this obstacle by employing chemical modifications to tailor SAs, thereby achieving targeted and light‐controlled antimicrobial effects. By conducting atomic‐level modifications on palladium SAs using glutathione (GSH) and mercaptophenylboronic acid (MBA), their superior targeted binding capabilities toward Escherichia coli cells are demonstrated, surpassing those of SAs modified with cysteine (Cys). Moreover, these modified SAs effectively inhibit wound bacteria proliferation and promote wound healing in rats, without inducing noticeable toxicity to major organs under 808 nm laser irradiation. This study highlights the significance of chemical engineering in tailoring the antibacterial properties of SA nanoparticles, opening avenues for combating bacterial infections and advancing nanoparticle‐based therapies.
Optimal Irreversible Electroporation Combined with Nano‐Enabled Immunomodulatory to Boost Systemic Antitumor Immunity
Authors: Peng Wencheng , Cao Yanbing , Zhang Yuting , Zhong Aoxue , Zhang Cao , Wei Zuwu , Liu Xiaolong , Dong Shoulong , Wu Jingcheng , Xue Yanan , Wu Ming , Yao Chenguo
Published: December 2023

In this work, we proposed nµPEF, a novel pulse configuration combining nanosecond and microsecond pulses (nµPEF), to enhance tumor ablation in irreversible electroporation (IRE) for oncological therapy. nµPEF demonstrated improved efficacy in inducing immunogenic cell death, positioning it as a potential candidate for next‐generation ablative therapy. However, the immune response elicited by nµPEF alone was insufficient to effectively suppress distant tumors. To address this limitation, we developed PPR@CM‐PD1, a genetically engineered nanovesicle. PPR@CM‐PD1 employed a polyethylene glycol‐polylactic acid‐glycolic acid (PEG‐PLGA) nanoparticle encapsulating the immune adjuvant imiquimod and coated with a genetically engineered cell membrane expressing programmed cell death protein 1 (PD1). This design allowed PPR@CM‐PD1 to target both the innate immune system through toll‐like receptor 7 (TLR7) agonism and the adaptive immune system through programmed cell death protein 1/programmed cell death‐ligand 1 (PD1/PDL1) checkpoint blockade. In turn, nµPEF facilitated intratumoral infiltration of PPR@CM‐PD1 by modulating the tumor stroma. The combination of nµPEF and PPR@CM‐PD1 generated a potent and systemic antitumor immune response, resulting in remarkable suppression of both nµPEF‐treated and untreated distant tumors (abscopal effects). This interdisciplinary approach presents a promising perspective for oncotherapy and holds great potential for future clinical applications.
Multiscale Heterogeneous Polymer Composites for High Stiffness 4D Printed Electrically Controllable Multifunctional Structures
Authors: Morales Ferrer Javier M. , Sánchez Cruz Ramón E. , Caplan Sophie , van Rees Wim M. , Boley J. William
Published: December 2023

4D printing is an emerging field where 3D printing techniques are used to pattern stimuli‐responsive materials to create morphing structures, with time serving as the fourth dimension. However, current materials utilized for 4D printing are typically soft, exhibiting an elastic modulus (E) range of 10−4 to 10 MPa during shape change. This restricts the scalability, actuation stress, and load‐bearing capabilities of the resulting structures. To overcome these limitations, multiscale heterogeneous polymer composites are introduced as a novel category of stiff, thermally responsive 4D printed materials. These inks exhibit an E that is four orders of magnitude greater than that of existing 4D printed materials and offer tunable electrical conductivities for simultaneous Joule heating actuation and self‐sensing capabilities. Utilizing electrically controllable bilayers as building blocks, a flat geometry that morphs into a 3D self‐standing lifting robot is designed and printed, setting new records for weight‐normalized load lifted and actuation stress when compared to other 3D printed actuators. Furthermore, this ink palette is employed to create and print planar lattice structures that transform into various self‐supporting complex 3D shapes. Finally these inks are integrated into a 4D printed electrically controlled multigait crawling robotic lattice structure that can carry 144 times its own weight.
A Hybrid Upper‐Arm‐Geared Exoskeleton with Anatomical Digital Twin for Tangible Metaverse Feedback and Communication
Authors: Ha Minhyeok , Lee Jihun , Cho Yongbeom , Lee Minwoo , Baek Hyunwoo , Lee Jungmin , Seo Jongmin , Chun Sejoon , Kim Kisoo , Kim Jin‐Gyun , Lee Won Gu
Published: December 2023

The pandemic coincided with rapid advancements in virtual reality (VR) and mixed reality (MR) in healthcare. The idea of virtually replicating the real world and its associated experiences has garnered significant attention under the newly coined term “metaverse.” The metaverse serves as a communication platform that integrates physical and virtual experiences. However, the lack of physical interaction between users and virtual environments remains an obstacle. This study introduces a hybrid upper‐arm‐geared exoskeleton system that combines an anatomical digital‐twin model with tangible VR torque feedback and an MR remote healthcare monitoring in a musculoskeletal interface device format. The device employs a dual epicyclic geared motor actuator capable of exerting torque feedback. It derived torque profiles that simulate physical interactions with hysteretic damping in the virtual environment. An anatomical digital twin model is also incorporated into the fabricated device in an MR format and assessed the device's performance using electromyogram and thermographic sensors. In addition, it evaluated haptic fidelity and versatility as an immersive metaverse wearable and performed support vector machine‐based analysis for motion feature classification. It believes this approach has the potential to be highly beneficial for providing tangible metaverse feedback and communication combined with a human‐informed digital‐twin model for remote healthcare monitoring in the postpandemic era.
Machine Learning Designed and Experimentally Confirmed Enhanced Reflectance in Aperiodic Multilayer Structures
Authors: Roy Chowdhury Prabudhya , Khot Krutarth , Song Jiawei , He Zihao , Kortge David , Han Zherui , Bermel Peter , Wang Haiyan , Ruan Xiulin
Published: December 2023

Machine learning (ML) methods have gained widespread attention in optimizing nanostructures for target transport properties and discovering unexpected physics. Here, an ML method is developed to discover and experimentally confirm binary CeO2‐MgO aperiodic multilayers (AMLs) for thermal barrier coatings with significantly enhanced reflectance. The effect of varying AML design parameters like total thickness, average period, and randomness in layer thicknesses, on the spectral and total reflectance is demonstrated. Introducing aperiodicity in layer thicknesses is shown to lead to a broadband increase in spectral reflectance due to photon localization. Since the number of possible AML structures increases exponentially with total thickness, a Genetic Algorithm optimizer is developed to efficiently discover AMLs with enhanced reflectance, for total thicknesses of 5–50 µm. Surprisingly, all the optimized structures show an odd number of layers with a CeO2 layer at both ends, deviating from the traditional way of designing binary superlattices with paired layers. The optimized AML and a reference periodic superlattice of 5 µm thickness are fabricated by Pulsed Laser Deposition and characterized by optical reflectance measurements. The fabricated AML, despite considerable fabrication uncertainty, still enhances the reflectance to 48% from 40% of the reference superlattice, validating the effectiveness of our ML‐based optimization process.
Colorful Semitransparent Organic Photovoltaics with Record Key Parameters by Optimizing Photon Utilization and Fabry‐Pérot Resonator Electrode
Authors: Xu Chunyu , Zhao Zijin , Kan Lixuan , Tao Sheng , Ma Xiaoling , Zhu Xixiang , Wang Kai , Zhang Jian , Li Junming , Zhang Fujun
Published: December 2023

Donor PM6 and acceptor L8‐BO are employed to build semitransparent organic photovoltaics (ST‐OPVs). Opaque OPVs are fabricated by tuning the spin‐coating speed of PM6:L8‐BO solution to optimize the photon utilization by balancing photon harvesting and photogenerated carrier collection. The optimal opaque OPVs exhibit relatively high fill‐factor (FF) of 77.58% and power conversion efficiency (PCE) of 15.07%, the average visible transmittance (AVT) of corresponding PM6:L8‐BO films arrives to 53.25%, indicating great potential in realizing efficient ST‐OPVs. ST‐OPVs are built with 1 nm Au/(10, 15, 20, 25 nm) Ag as cathode, exhibiting the PCE/AVT of 11.53%/22.57%, 13.20%/14.24%, 14.28%/9.34%, and 14.71%/6.77%, respectively. Colorful ST‐OPVs are achieved by coupling different Ag/LiF/Ag Fabry‐Pérot (F‐P) resonator microcavity. Green ST‐OPVs with varied color coordinates are achieved by fixing LiF layer thickness as 110 nm and varying Ag layers′ thickness, originating from the adjusted transmittance spectra of green ST‐OPVs. Upon fixing Ag layers′ thickness as 15/25 nm and varying LiF layer thickness as 90, 110, and 145 nm, ST‐OPVs present colors of blue, green, and red with corresponding transmittance peak at 474, 553, and 657 nm. The corresponding PCE/peak transmittance (Tpeak) values arrive to 13.80%/37.8%, 13.31%/28.4%, and 13.20%/27.7%, which should be the best performance among reported colorful ST‐OPVs.
Impaired Detoxification of Trans, Trans‐2,4‐Decadienal, an Oxidation Product from Omega‐6 Fatty Acids, Alters Insulin Signaling, Gluconeogenesis and Promotes Microvascular Disease
Authors: Qian Xin , Klatt Stephan , Bennewitz Katrin , Wohlfart David Philipp , Lou Bowen , Meng Ye , Buettner Michael , Poschet Gernot , Morgenstern Jakob , Fleming Thomas , Sticht Carsten , Hausser Ingrid , Fleming Ingrid , Szendroedi Julia , Nawroth Peter Paul , Kroll Jens
Published: December 2023

Omega‐6 fatty acids are the primary polyunsaturated fatty acids in most Western diets, while their role in diabetes remains controversial. Exposure of omega‐6 fatty acids to an oxidative environment results in the generation of a highly reactive carbonyl species known as trans, trans‐2,4‐decadienal (tt‐DDE). The timely and efficient detoxification of this metabolite, which has actions comparable to other reactive carbonyl species, such as 4‐hydroxynonenal, acrolein, acetaldehyde, and methylglyoxal, is essential for disease prevention. However, the detoxification mechanism for tt‐DDE remains elusive. In this study, the enzyme Aldh9a1b is identified as having a key role in the detoxification of tt‐DDE. Loss of Aldh9a1b increased tt‐DDE levels and resulted in an abnormal retinal vasculature and glucose intolerance in aldh9a1b−/− zebrafish. Transcriptomic and metabolomic analyses revealed that tt‐DDE and aldh9a1b deficiency in larval and adult zebrafish induced insulin resistance and impaired glucose homeostasis. Moreover, alterations in hyaloid vasculature is induced by aldh9a1b knockout or by tt‐DDE treatment can be rescued by the insulin receptor sensitizers metformin and rosiglitazone. Collectively, these results demonstrated that tt‐DDE is the substrate of Aldh9a1b which causes microvascular damage and impaired glucose metabolism through insulin resistance.
Reinforcement Learning‐Guided Long‐Timescale Simulation of Hydrogen Transport in Metals
Authors: Tang Hao , Li Boning , Song Yixuan , Liu Mengren , Xu Haowei , Wang Guoqing , Chung Heejung , Li Ju
Published: December 2023

Diffusion in alloys is an important class of atomic processes. However, atomistic simulations of diffusion in chemically complex solids are confronted with the timescale problem: the accessible simulation time is usually far shorter than that of experimental interest. In this work, long‐timescale simulation methods are developed using reinforcement learning (RL) that extends simulation capability to match the duration of experimental interest. Two special limits, RL transition kinetics simulator (TKS) and RL low‐energy states sampler (LSS), are implemented and explained in detail, while the meaning of general RL are also discussed. As a testbed, hydrogen diffusivity is computed using RL TKS in pure metals and a medium entropy alloy, CrCoNi, and compared with experiments. The algorithm can produce counter‐intuitive hydrogen‐vacancy cooperative motion. We also demonstrate that RL LSS can accelerate the sampling of low‐energy configurations compared to the Metropolis–Hastings algorithm, using hydrogen migration to copper (111) surface as an example.
Identifying Stable Electrocatalysts Initialized by Data Mining: Sb2WO6 for Oxygen Reduction
Authors: Jia Xue , Yu Zixun , Liu Fangzhou , Liu Heng , Zhang Di , Campos dos Santos Egon , Zheng Hao , Hashimoto Yusuke , Chen Yuan , Wei Li , Li Hao
Published: December 2023

Data mining from computational materials database has become a popular strategy to identify unexplored catalysts. Herein, the opportunities and challenges of this strategy are analyzed by investigating a discrepancy between data mining and experiments in identifying low‐cost metal oxide (MO) electrocatalysts. Based on a search engine capable of identifying stable MOs at the pH and potentials of interest, a series of MO electrocatalysts is identified as potential candidates for various reactions. Sb2WO6 attracted the attention among the identified stable MOs in acid. Based on the aqueous stability diagram, Sb2WO6 is stable under oxygen reduction reaction (ORR) in acidic media but rather unstable under high‐pH ORR conditions. However, this contradicts to the subsequent experimental observation in alkaline ORR conditions. Based on the post‐catalysis characterizations, surface state analysis, and an advanced pH‐field coupled microkinetic modeling, it is found that the Sb2WO6 surface will undergo electrochemical passivation under ORR potentials and form a stable and 4e‐ORR active surface. The results presented here suggest that though data mining is promising for exploring electrocatalysts, a refined strategy needs to be further developed by considering the electrochemistry‐induced surface stability and activity.
Regeneration of Thyroid Glands in the Spleen Restores Homeostasis in Thyroidectomy Mice
Authors: Tian Xue‐Jiao , Yin Zhi‐Jie , Li Zhen‐Jiang , Wang Zhen‐Zhen , Xing Zhen , Liu Chun‐Yan , Wang Lin‐Tao , Wang Chun‐Ming , Zhang Jun‐Feng , Dong Lei
Published: December 2023

Surgical removal of the thyroid gland (TG) for treating thyroid disorders leaves the patients on lifelong hormone replacement that partially compensates the physiological needs, but regenerating TG is challenging. Here, an approach is reported to regenerate TG within the spleen for fully restoring the thyroid's functions in mice, by transplanting thyroid tissue blocks to the spleen. Within 48 h, the transplanted tissue efficiently revascularizes, forming thyroid follicles similar to the native gland after 4 weeks. Structurally, the ectopically generated thyroid integrates with the surrounding splenic tissue while maintaining its integrity, separate from the lymphatic tissue. Functionally, it fully restores the native functions of the TG in hormone regulation in response to physiological stimuli, outperforming the established method of oral levothyroxine therapy in maintaining systemic homeostasis. The study demonstrates the full restoration of thyroid functions post‐thyroidectomy by intrasplenic TG regeneration, providing fresh insights for designing novel therapies for thyroid‐related disorders.
Nanoenabled Intracellular Metal Ion Homeostasis Regulation for Tumor Therapy
Authors: Xu Lihua , Peng Mingzheng , Gao Tingting , Wang Dandan , Lian Xiaowu , Sun Huihui , Shi Jinjin , Wang Yafeng , Wang Pengju
Published: December 2023

Endogenous essential metal ions play an important role in many life processes, especially in tumor development and immune response. The approval of various metallodrugs for tumor therapy brings more attention to the antitumor effect of metal ions. With the deepening understanding of the regulation mechanisms of metal ion homeostasis in vivo, breaking intracellular metal ion homeostasis becomes a new means to inhibit the proliferation of tumor cells and activate antitumor immune response. Diverse nanomedicines with the loading of small molecular ion regulators or metal ions have been developed to disrupt metal ion homeostasis in tumor cells, with higher safety and efficiency than free small molecular ion regulators or metal compounds. This comprehensive review focuses on the latest progress of various intracellular metal ion homeostasis regulation‐based nanomedicines in tumor therapy including calcium ion (Ca2+), ferrous ion (Fe2+), cuprous ion (Cu+), managanese ion (Mn2+), and zinc ion (Zn2+). The physiological functions and homeostasis regulation processes of ions are summarized to guide the design of metal ion regulation‐based nanomedicines. Then the antitumor mechanisms of various ions‐based nanomedicines and some efficient synergistic therapies are highlighted. Finally, the challenges and future developments of ion regulation‐based antitumor therapy are also discussed, hoping to provide a reference for finding more effective metal ions and synergistic therapies.
Three Birds, One Stone: An Osteo‐Microenvironment Stage‐Regulative Scaffold for Bone Defect Repair through Modulating Early Osteo‐Immunomodulation, Middle Neovascularization, and Later Osteogenesis
Authors: Yuan Yuhao , Xu Yan , Mao Yiyang , Liu Hongbin , Ou Minning , Lin Zhangyuan , Zhao Ruibo , Long Haitao , Cheng Liang , Sun Buhua , Zhao Shushan , Zeng Ming , Lu Bangbao , Lu Hongbin , Zhu Yong , Chen Can
Published: December 2023

In order to repair critical‐sized bone defects, various polylactic acid‐glycolic acid (PLGA)‐based hybrid scaffolds are successfully developed as bone substitutes. However, the byproducts of these PLGA‐based scaffolds are known to acidify the implanted site, inducing tiresome acidic inflammation. Moreover, these degradation productions cannot offer an osteo‐friendly microenvironment at the implanted site, matching natural bone healing. Herein, inspired by bone microenvironment atlas of natural bone‐healing process, an osteo‐microenvironment stage‐regulative scaffold (P80/D10/M10) is fabricated by incorporating self‐developed decellularized bone matrix microparticles (DBM‐MPs) and multifunctional magnesium hydroxide nanoparticles (MH‐NPs) into PLGA with an optimized proportion using low‐temperature rapid prototyping (LT‐RP) 3D‐printing technology. The cell experiments show that this P80/D10/M10 exhibits excellent properties in mechanics, biocompatibility, and biodegradability, meanwhile superior stimulations in osteo‐immunomodulation, angiogenesis, and osteogenesis. Additionally, the animal experiments determined that this P80/D10/M10 can offer an osteo‐friendly microenvironment in a stage‐matched pattern for enhanced bone regeneration, namely, optimization of early inflammation, middle neovascularization, and later bone formation. Furthermore, transcriptomic analysis suggested that the in vivo performance of P80/D10/M10 on bone defect repair is mostly attributed to regulating artery development, bone development, and bone remodeling. Overall, this study reveals that the osteo‐microenvironment stage‐regulative scaffold provides a promising treatment for bone defect repair.
Additively Manufactured Zn‐2Mg Alloy Porous Scaffolds with Customizable Biodegradable Performance and Enhanced Osteogenic Ability
Authors: Wang Xuan , Liu Aobo , Zhang Zhenbao , Hao Dazhong , Liang Yijie , Dai Jiabao , Jin Xiang , Deng Huanze , Zhao Yantao , Wen Peng , Li Yanfeng
Published: December 2023

The combination of bioactive Zn‐2Mg alloy and additively manufactured porous scaffold is expected to achieve customizable biodegradable performance and enhanced bone regeneration. Herein, Zn‐2Mg alloy scaffolds with different porosities, including 40% (G‐40‐2), 60% (G‐60‐2), and 80% (G‐80‐2), and different unit sizes, including 1.5 mm (G‐60‐1.5), 2 mm (G‐60‐2), and 2.5 mm (G‐60‐2.5), are manufactured by a triply periodic minimal surface design and a reliable laser powder bed fusion process. With the same unit size, compressive strength (CS) and elastic modulus (EM) of scaffolds substantially decrease with increasing porosities. With the same porosity, CS and EM just slightly decrease with increasing unit sizes. The weight loss after degradation increases with increasing porosities and decreasing unit sizes. In vivo tests indicate that Zn‐2Mg alloy scaffolds exhibit satisfactory biocompatibility and osteogenic ability. The osteogenic ability of scaffolds is mainly determined by their physical and chemical characteristics. Scaffolds with lower porosities and smaller unit sizes show better osteogenesis due to their suitable pore size and larger surface area. The results indicate that the biodegradable performance of scaffolds can be accurately regulated on a large scale by structure design and the additively manufactured Zn‐2Mg alloy scaffolds have improved osteogenic ability for treating bone defects.
Kinkless Electronic Junction along 1D Electronic Channel Embedded in a Van Der Waals Layer
Authors: Yao Qirong , Park Jae Whan , Won Choongjae , Cheong Sang‐Wook , Yeom Han Woong
Published: December 2023

Here, the formation of type‐I and type‐II electronic junctions with or without any structural discontinuity along a well‐defined 1 nm‐wide 1D electronic channel within a van der Waals layer is reported. Scanning tunneling microscopy and spectroscopy techniques are employed to investigate the atomic and electronic structure along peculiar domain walls formed on the charge‐density–wave phase of 1T‐TaS2. Distinct kinds of abrupt electronic junctions with discontinuities of the band gap along the domain walls are found, some of which even do not have any structural kinks and defects. Density‐functional calculations reveal a novel mechanism of the electronic junction formation; they are formed by a kinked domain wall in the layer underneath through substantial electronic interlayer coupling. This work demonstrates that the interlayer electronic coupling can be an effective control knob over nanometer‐scale electronic property of 2D atomic monolayers.
Deposition of Sodium Metal at the Copper‐NaSICON Interface for Reservoir‐Free Solid‐State Sodium Batteries
Authors: Ortmann Till , Fuchs Till , Eckhardt Janis K. , Ding Ziming , Ma Qianli , Tietz Frank , Kübel Christian , Rohnke Marcus , Janek Jürgen
Published: December 2023

“Anode‐free” solid‐state battery concepts are explored extensively as they promise a higher energy density with less material consumption and simple anode processing. Here, the homogeneous and uniform electrochemical deposition of alkali metal at the interface between current collector and solid electrolyte plays the central role to form a metal anode within the first cycle. While the cathodic deposition of lithium has been studied intensively, knowledge on sodium deposition is scarce. In this work, dense and uniform sodium layers of several microns thickness are deposited at the Cu|Na3.4Zr2Si2.4P0.6O12 interface with high reproducibility. At current densities of ≈1 mA∙cm−2, relatively uniform coverage is achieved underneath the current collector, as shown by electrochemical impedance spectroscopy and 3D confocal microscopy. In contrast, only slight variations of the coverage are observed at different stack pressures. Early stages of the sodium metal growth are analyzed by in situ transmission electron microscopy revealing oriented growth of sodium. The results demonstrate that reservoir‐free (“anode‐free”) sodium‐based batteries are feasible and may stimulate further research efforts in sodium‐based solid‐state batteries.
Cross‐kingdom regulation by plant‐derived miRNAs in mammalian systems
Authors: Yang Linpu , Feng Han
Published: December 2023

MicroRNAs (miRNAs) are small noncoding RNA molecules ubiquitously distributed across diverse organisms, serving as pivotal regulators of genetic expression. Notably, plant‐derived miRNAs have been demonstrated to have unique bioactivity and certain stability in mammalian systems, thereby facilitating their capacity for cross‐kingdom modulation of gene expression. While there is substantial evidence supporting the regulation of mammalian cells by plant‐derived miRNAs, several questions remain unanswered. Specifically, a comprehensive investigation of the mechanisms underlying the stability and transport of plant miRNAs and their cross‐kingdom regulation of gene expression in mammals remains to be done. In this review, we summarized the origin, processing, and functional mechanisms of plant miRNAs in mammalian tissues and circulation, emphasizing their greater resistance to mammalian digestion and circulation systems compared to animal miRNAs. Additionally, we introduce four well‐known plant miRNAs that have been extensively studied for their functions and mechanisms in mammalian systems. By delving into these aspects, we aim to offer a fundamental understanding of this intriguing field and shed light on the complex interactions between plant miRNAs and mammalian biology.
Colloidal Self‐Assembly: From Passive to Active Systems
Authors: Huang Yaxin , Wu Changjin , Chen Jingyuan , Tang Jinyao
Published: December 2023

Self‐assembly fundamentally implies the organization of small sub‐units into large structures or patterns without the intervention of specific local interactions. This process is commonly observed in nature, occurring at various scales ranging from atomic/molecular assembly to the formation of complex biological structures. Colloidal particles may serve as micrometer‐scale surrogates for studying assembly, particularly for the poorly understood kinetic and dynamic processes at the atomic scale. Recent advances in colloidal self‐assembly have enabled the programmable creation of novel materials with tailored properties. We here provide an overview and comparison of both passive and active colloidal self‐assembly, with a discussion on the energy landscape and interactions governing both types. In the realm of passive colloidal assembly, many impressive and important structures have been realized, including colloidal molecules, one‐dimensional chains, two‐dimensional lattices, and three‐dimensional crystals. In contrast, active colloidal self‐assembly, driven by optical, electric, chemical, or other fields, involves more intricate dynamic processes, offering more flexibility and potential new applications. A comparative analysis underscores the critical distinctions between passive and active colloidal assemblies, highlighting the unique collective behaviors emerging in active systems. These behaviors encompass collective motion, motility‐induced phase segregation, and exotic properties arising from out‐of‐equilibrium thermodynamics. Through this comparison, we aim to identify the future opportunities in active assembly research, which may suggest new application domains.
A General Method to Access Sterically Encumbered Geminal Bis(boronates) via Formal Umpolung Transformation of Terminal Diboron Compounds
Authors: Ning Peng‐Fei , Wei Yi , Chen Xin‐Yi , Yang Yi‐Fei , Gao Feng‐Chen , Hong Kai
Published: December 2023

General methods for the preparation of geminal bis(boronates) are of great interest due to their widespread applications in organic synthesis. While the terminal gem‐diboron compounds are readily accessible, the construction of the sterically encumbered, internal analogues has remained a prominent challenge. Herein, we report a formal umpolung strategy to access these valuable building blocks. The readily available 1,1‐diborylalkanes were first converted into the corresponding α‐halogenated derivatives, which then serve as electrophilic components, undergoing a formal substitution with a diverse array of nucleophiles to form a series of C−C, C−O, C−S, and C−N bonds. This protocol features good tolerance to steric hindrance and a wide variety of functional groups and heterocycles. Notably, this strategy can also be extended to the synthesis of diaryl and terminal gem‐diboron compounds, therefore providing a general approach to various types of geminal bis(boronates).
A donor–acceptor (D–A) conjugated polymer for fast storage of anions
Authors: Fu Manli , Chen Yuan , Jin Weihao , Dai Huichao , Zhang Guoqun , Fan Kun , Gao Yanbo , Guan Linnan , Chen Jizhou , Zhang Chenyang , Ma Jing , Wang Chengliang
Published: December 2023

Organic electrode materials have attracted a lot interest in batteries in recent years. However, most of them still suffer from low performance such as low electrode potential, slow reaction kinetics, and short cycle life. In this work, we report a strategy of fabricating donor–acceptor (D–A) conjugated polymers for facilitating the charge transfer and therefore accelerating the reaction kinetics by using the copolymer (p‐TTPZ) of dihydrophenazine (PZ) and thianthrene (TT) as a proof‐of‐concept. The D–A conjugated polymer as p‐type cathode could store anions and exhibited high discharge voltages (two plateaus at 3.82 V, 3.16 V respectively), a reversible capacity of 152 mAh g−1 at 0.1 A g−1, excellent rate performance with a high capacity of 124.2 mAh g−1 at 10 A g−1 (≈50 C) and remarkable cyclability. The performance, especially the rate capability was much higher than that of its counterpart homopolymers without D–A structure. As a result, the p‐TTPZ//graphite full cells showed a high output voltage (3.26 V), a discharge specific capacity of 139.1 mAh g−1 at 0.05 A g−1 and excellent rate performance. This work provides a novel strategy for developing high performance organic electrode materials through molecular design and will pave a way towards high energy density organic batteries.
Effects of ionic liquids as catalysts on liquid crystal aromatic polyester based on thin‐film polymerization technique
Authors: Wu Zexi , Shi Caijie , Peng Tao , Cheng Qiannan , Tang Qingquan , Wang Luoxin , Wang Hua , Xiong Siwei
Published: December 2023

Liquid crystal aromatic polyesters (LCAPs) have been used in wide applications, such as chip packaging and airship skin. The traditional polymerization of LCAP is catalyzed by inorganic salts, for example, sodium acetate. Herein, we reported three kinds of ionic liquids (ILs) as catalysts to promote LCAP polymerization for the first time. The effects of ILs on the polymerization behaviors are investigated by in situ observing the liquid crystal (LC) phase behaviors based on the thin‐film polymerization technique. The evolution of LC phase over time was detailly investigated by analyzing the emergence, fusion, and growth of LC phase. The temperature from 170 to 210°C and the catalyst concentration in range from 0 to 0.5 wt% are compared, showing that temperature at 210°C and catalyst concentration at 0.5 wt% are the best polymerization conditions for all ILs catalysts. In comparison with trimethylsulfonium iodide and piperidine acetate, 1‐ethyl‐3‐methylimidazolium acetate has the best catalytic effect for the polymerization of LCAP in all experimental conditions. The successful polymerization was confirmed by FT‐IR spectra, showing the increased intensity of vibration peak at 1735 cm−1 attributed to the generation of ester groups while the decreased intensities of vibration peaks at 1759 and 1370 cm−1.
Quantitative assessment of polymer molecular shape based on changes in the slope of the Mark‐Houwink plot derived from size‐exclusion chromatography with triple detection
Authors: Bos Tijmen S. , Philipsen Harry J. A. , Staal Bastiaan B. P. , Purmova Jindra , Beerends René J. L. , Buijtenhuijs Ab , Karlson Leif , Schoenmakers Peter J. , Somsen Govert W.
Published: December 2023

A new approach is presented for gaining additional insights from the molecular weight distribution and intrinsic viscosity of polymers as obtained using size‐exclusion chromatography in combination with refractive index, viscometry, and multiangle light scattering detectors. The approach allows for a more quantitative interpretation of the Mark‐Houwink plot by assessing the variation of the slope as a function of molecular weight. No prior information on the inter‐ and intramolecular interactions of the polymer is needed. The proposed curvature parameter can be correlated to the structural and chemical properties (e.g., branching, composition, randomness) of the polymer. The influence of the covered molecular weight interval and the sample concentration on the precision of the method was studied. This new workflow can be utilized to assess the effect of the solvent system and conditions on the solvation behavior of polymers. To evaluate the applicability of the workflow, three case studies have been performed, including an analysis of ethylene‐propylene‐diene monomer, cellulose ether, and polyamide‐4,10 samples. In addition, an open‐access tool is provided, to aid polymer researchers in incorporating this approach in their work. The developed method can be used to quickly investigate whether an industrial polymer batch contains unwanted branched species or exhibits particular solvation behavior.
High erosion resistance thermoplastic polyurethanes composites fabricated via intercalation reinforced interfacial interaction
Authors: Ma Yuji , Cui Xiaofeng , Huang Ming , Zhang Na , Gao Guoli , Liu Shihai
Published: December 2023

The weak interface and poor dispersion of carbon nanofillers in polymer matrix composites lead to a significant decrease in their performance, restricting the development of polymer nanocomposites. In this work, a highly facile strategy has been developed to improve the interfacial adhesion performance between graphene nanoplates (GNP) and thermoplastic polyurethanes (TPU) matrix via self‐polymerization of dopamine. Then, single‐walled carbon nanotubes (CNT), as reinforcing agent, were introduced into surface modified GNP solution to prepare the corresponding ternary composites. Scanning electron microscope images show that GNP and CNT formed 3‐D interconnecting network‐like architecture. The sample modified with three layers of nonwoven fabric decorated with 1.0 mg/mL nanomaterial exhibit a tensile strength 35% higher than that of the virgin TPU. Consequently, compared with virgin TPU, the erosion resistance and thermal conductivity are enhanced by 78% and 45%, respectively.
Investigating the relationship between cranial bone thickness and diploic channels: A first comparison between fossil Homo sapiens and Homo neanderthalensis
Authors: Hui Jiaming , Balzeau Antoine
Published: December 2023

Diploic veins are part of the circulatory system of the head. They transport venous blood and cerebrospinal fluid and are housed in diploic channels (DCs). DCs are highly variable in terms of their position, extension, and size. These parameters were hypothesized to be related to the variations in cranial vault thickness (CVT). For the first time, we analyzed the spatial relationship between CVT and DCs in a sample of eight H. neanderthalensis and H. sapiens cranial fossils. Using micro‐CT scanning data, we constructed color maps of the CVT and visually inspected whether the regional thickness variation was associated with the morphology and distribution of the DC branches. The results showed that when regional bone thickness was below a certain threshold, no DCs or scattered small DC branches were present. Larger DC branches appeared only when the thickness exceeded the threshold. However, once the threshold was reached, further increases in thickness no longer resulted in more or larger DCs. This study also found that our sample of H. neanderthalensis and H. sapiens have different distribution patterns in thin areas, which may affect how their DCs connect with different branches of the middle meningeal vessels. This preliminary study provides evidence for the discussion on the interaction between the cranium, brain, and blood vessels. Future research should include more hominin fossils to better document the variation within each species and possible evolutionary trends among hominin lineages.
Synthesis of High‐Fluorescent Diphenyl−anthracene Derivatives and Application in Detection of Nitroaromatic Explosives and Fingerprint Identification
Authors: Lai Jiagen , Pan Qinghua , Ma Qingfang , Shan Xiaoyue , Chen Lian , Gao Jianhua
Published: December 2023

The development of high‐intensity fluorescent materials is always the focuses and forefront projects because of their important applications in displays, sensing and detection fields. In recent years, the detection of explosives has attracted increasing attention due to security and counterterrorism issues. Herein, two diphenyl−anthracene (DPA) derivatives were designed and synthesized by introducing strong electron withdrawing fluorine atoms and cyano‐groups to DPA, which exhibited strong fluorescence both in the solution and solid phase with the absolute quantum yields up to 70.4 % and 45.9 % respectively. The detection behavior of nitroaromatic explosives such as picric acid (PA), 2,4,6‐trinitrotoluene (TNT) and 3‐Nitropropionic acid (3‐NP) also shows good sensitivity with the quenching constant as high as 6.3×104 L mol−1. Theoretical calculation demonstrates that the fluorescence quenching behavior of the two DPA derivatives is caused by the behavior of photoinduced electron transfer (PET) and the resonance energy transfer (RET) studies explained the higher sensitivity and selectivity of both compounds towards PA than other nitro‐containing explosives. Furthermore, the strong solid‐state fluorescence of the DPA derivatives also shows excellent advantages in enhancing latent fingerprint recognition.
A critical look at adjusted fetal weights in rats
Authors: Wise L. David , DeSesso John M.
Published: December 2023

Background

A new derived (i.e., calculated) endpoint of developmental toxicology has appeared in a very few studies since 1990. This endpoint is adjusted mean live fetal weight per litter or adjusted fetal weight. Given our lack of familiarity with the endpoint, we evaluated the basis, prevalence, methods, and usefulness in embryo‐fetal developmental toxicity (EFDT) studies in rats.

Methods

Literature searches were performed with key terms using PubMed and Google Scholar. Major textbooks were consulted but lack of any mention of the endpoint. Unpublished EFDT data, which are readily available online, were utilized to test adjustment methods.

Results

Pertinent information on factors that influence fetal weight goes back a century. Four papers utilizing rats were found in which fetal weights were adjusted using either statistical or formula‐based methods to adjust fetal weights. Only one study showed a clear benefit to the endpoint when there was a marked decrease in live litter size; this pointed to situations in which the new endpoint might be useful. The lone formula‐based adjustment method was found to be lacking adequate testing and justifications. A new experimental alternative formula‐based adjustment is shown to produce results very similar to statistical methods.

Conclusions

From this assessment, we recommend that adjusted fetal weight should not be a routine endpoint at this time. However, there are likely cases where this derived endpoint could aid interpretation. We encourage other investigators to examine previous EFDT study data to establish guidance on the use of adjusted mean live fetal weights.
A signal‐switchable fluorescent probe for detection of HPO42− based on 5,10,15,20‐(4‐sulphonatophenyl)porphyrin (TPPS4)
Authors: Mu Wencheng , Li Jing , Wang Siying , Ma Tianfeng , Shi Lin , Xu Xiaohua , Lu Yongchang , Wang Huan
Published: December 2023

In this study, 5,10,15,20‐(4‐sulphonatophenyl)porphyrin (TPPS4) was selected as a fluorescent probe due to its excellent characteristics including high quantum yield, good water solubility, and exceptional biocompatibility. With an excitation wavelength set at 515 nm, the optimal fluorescence emission wavelength for TPPS4 was measured at 642 nm. At this moment, the fluorescence signal of TPPS4 pink solution was in the ‘ON’ state. The fluorescence intensity of TPPS4 was quenched when ascorbic acid (AA) was introduced, which was due to the electron transfer quenching effect between AA and TPPS4. The colour of the corresponding solution changed from pink to green, and the fluorescence signal was in the ‘OFF’ state. When HPO42− was further introduced into the TPPS4–AA system, the quenched fluorescence intensity of TPPS4 was recovered due to the unique interaction between HPO42− and AA. At this time, the colour of the corresponding solution changed from green to red, and the fluorescence signal was in the ‘ON’ state. Therefore, an ‘ON–OFF–ON’ signal‐switchable fluorescent probe was constructed based on TPPS4 to detect HPO42−. The results showed that the linear range of HPO42− was 4.0 × 10−9 to 1.7 × 10−6 M, and the detection limit was 1.3 × 10−9 M (S/N = 3). The sensing system exhibited high accuracy and sensitivity, and it could be used successfully to detect HPO42− in real samples.