bluuebunny/crossref_metadata_2025 huggingface dataset:
3D Printing of Mechanically Elastic, Self‐Adhesive, and Biocompatible Organohydrogels for Wearable and Breathable Strain Sensors
Authors: Guo Binbin , Zhong Yukun , Song Xiaoxia , Chen Xiaoteng , Zhou Peng , Zhao Fuxin , Bai Jiaming
Published: December 2022

Organohydrogel‐based strain sensors have gained increasing attention in the fields of real‐time healthcare and motion detection due to their excellent flexibility, stretchability, and skin‐like compliance. However, the fundamental attributes, such as mechanical elasticity, self‐adhesiveness, and biocompatibility, are challenging to be simultaneously obtained in organohydrogels, limiting their applications in wearable electronics. Additionally, traditional organohydrogels need to be fixed to the surface of the human skin and suffer from inferior breathability, resulting in complicated operations and severe uncomfortableness, respectively. Herein, a multifunctional organohydrogel is designed for wearable strain sensor by a facile digital light processing (DLP) 3D printing technology. By rationally tailoring the chemical (poly(N‐acryloylmorpholine)/poly(ethylene glycol) diacrylate) and physical (poly(N‐acryloylmorpholine)/poly(ethylene glycol) diacrylate and glycerin/water) cross‐linking networks, the organohydrogel exhibits promising water absorption/retention, high stretchability, impressive elasticity, and promising fatigue resistance. Additionally, good ionic conductivity, inherent self‐adhesiveness, and biocompatibility are simultaneously achieved. On the basis of the multifunctionalities, 3D multihole organohydrogels are designated as wearable and breathable strain sensors, facilitating the manipulation without any fixation and increasing the wear comfortableness. It is believed that 3D printed multihole organohydrogels show great potential in wearable flexible electronics.
Selective Release of Excitatory‐Inhibitory Neurotransmitters Emulated by Unipolar Synaptic Transistors via Gate Voltage Amplitude Modulation
Authors: Chen Ye , Hua Jing , Li Yueqing , Zhang Qi , Shao He , Li Wen , Ling Haifeng , Xu Xiangxing , Huang Wei , Yi Mingdong
Published: December 2022

Organic field‐effect transistor (OFET) memory devices are benefiting from their independent gate modulation advantages for hardware implementation of synaptic functionalities. However, the imitation of selective release of excitatory–inhibitory neurotransmitters in a unipolar synaptic OFET is challenging due to the unbalanced mobile carrier concentration. Here, a p‐type synaptic OFET memory with CsPbBr3 quantum dots (QDs) as nano‐floating gates (NFGs) is developed, which can emulate both the excitatory–inhibitory responses of the biological synapse and their reconfigurable nature. By controlling the offset difference between stimulus voltage and reading voltage, the concomitant and independently expressed excitatory and inhibitory responses are successfully implemented in a negative gate modulation manner, but without introducing an ambipolar semiconductor or additional optical terminal. This reconfigurable modulation is ascribed to the dynamic competition between external electric field and built‐in electric field assisted by charge trapping in shallow traps. The proposed gate voltage‐offset method can be generally adapted to other unipolar synaptic OFETs. These results provide insight into OFET memory devices for building neuromorphic hardware elements with tailorable synaptic plasticity.
Recent Progress and Challenges of Bismuth‐Based Halide Perovskites for Emerging Optoelectronic Applications
Authors: Chen Xu , Jia Mochen , Xu Wen , Pan Gencai , Zhu Jinyang , Tian Yongtao , Wu Di , Li Xinjian , Shi Zhifeng
Published: December 2022

Recently, metal halide perovskites have attracted extensive attentions owing to their superior optoelectronic properties in various device applications, such as solar cells, photodetectors, light‐emitting diodes, lasing, photocatalysis, etc. Up to now, the state‐of‐the‐art developments of perovskite‐based devices are most using the lead‐halide perovskite system. However, the presence of lead (Pb) in these devices, which is insidious bioaccumulative hazard to human bodies, and a poor stability against light, heat, and humidity hamper their practical applications and future commercialization. Therefore, the scientific community is searching for low‐toxicity and environmental‐friendly lead‐free perovskite‐type materials as a back‐up strategy. Among the possible Pb‐substitution strategies, the trivalent bismuth cation (Bi3+) possesses the same electronic configuration as Pb2+, and some emerging Bi‐based perovskites and derivatives are experimentally characterized, which exhibit comparable optoelectronic properties to the Pb‐based perovskites. In this review, a comprehensive overview of currently explored Bi‐based halide perovskites is reported, with an emphasis on their synthesis methods, structural diversity, photophysical properties, and their current and potential applications in various optoelectronic categories. Finally, this review is finished with a critical outlook into the current challenges and development prospects of Bi‐based halide perovskites toward the versatile optoelectronic applications.
Efficient and Thermally Robust Broadband Near‐Infrared Emission in a Garnet Ca3MgHfGe3O12:Cr3+ Phosphor
Authors: Li Chaojie , Zhong Jiyou
Published: December 2022

Near‐infrared (NIR) spectroscopy based on phosphor‐converted light‐emitting‐diode (pc‐LED) has promising applications in food quality analysis, security monitoring, medical diagnosis, and bioimaging fields, stimulating the demand of developing NIR phosphors with high‐performance. Herein, a highly efficient and thermally robust Ca3MgHfGe3O12:Cr3+ NIR phosphor is discovered, which exhibits a broadband NIR emission (λem = 800 nm) covering 700 to 1100 nm region with an internal quantum efficiency as high as 90.7% when excited by 460 nm blue light. Moreover, the emission intensity at 423 K retains 84.5% of that at room temperature. The highly efficient and thermally robust luminescence of this material is mainly ascribed to the ultrawide bandgap of host, extremely weak electron–photon coupling effect, defect‐free, and highly structural rigidity. The NIR pc‐LED device fabricated by using the optimized Ca3Mg0.97Hf0.97Ge3O12:0.06Cr3+ phosphor combined with blue (λem = 455 nm) LED chip produces an excellent NIR output power of 49.5 mW @ 11.5% under a driving current of 150 mA, which indicates a superiority to the device fabricated by using the well‐known efficient ScBO3:Cr3+ phosphor under the same condition. Therefore, this work not only provides a promising broadband NIR material, but also highlights the design rules for searching high‐performance NIR materials toward spectroscopy applications.
Light‐Triggered Nickel‐Catalyzed Azide−Alkyne Cycloaddition for the Preparation of 1,5‐Disubstituted 1,2,3‐Triazoles
Authors: Abadie Baptiste , Almansa Axel , He Ouchan , Massip Stéphane , Molton Florian , Duboc Carole , Vincent Jean‐Marc
Published: December 2022

When irradiated by UVA, a Ni(II) precatalyst integrating a benzophenone chromophore in its structure catalyzes the regioselective cycloaddition of alkynes and azides to produce 1,5‐disubsituted 1,2,3‐triazoles with 1,5:1,4 regioisomer ratios ranging from 1.7:1 to >20:1. Speciation and reactivity studies revealed that the reaction most likely proceeds through a Ni(I)/Ni(III) catalytic cycle.

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Enantioselective Synthesis of Benzothiazolines from Fluoroalkyl Ketones Using Chiral Imidazoline−Phosphoric Acid Catalysts
Authors: Iizuka Yuka , Wada Tatsumi , Ogura Kazuki , Takehara Tsunayoshi , Suzuki Takeyuki , Nakamura Shuichi
Published: December 2022

The first enantioselective synthesis of cyclic N,S‐ketals having tetrasubstituted chiral center through intramolecular cyclization between carbonyl compounds and aminothiols has been developed. The reaction of fluoroalkyl ketones with aminobenzenethiols using a chiral imidazoline−phosphoric acid catalyst afforded products in high yields with high enantioselectivity. The observed enantioselectivity is explained using preliminary mechanistic information.

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Visible‐Light‐Driven Hydrophosphorylation of Azobenzenes Enabled by trans‐to‐cis Photoisomerization
Authors: Yang Jingya , Wang Cunhui , Zhou Hongyan , Kong Qianqian , Ma Wentong
Published: December 2022

A visible‐light‐driven hydrophosphorylation of azobenzenes with diarylphosphine oxides was successfully developed. The reaction proceeded smoothly under blue light irradiation at room temperature without any photocatalyst required, providing a mild approach for this transformation with new strategy. Of important note is that the visible light‐driven trans‐to‐cis photoisomerization of azobenzenes was found to be the key for the process of the reaction, highlighting this underestimated reactivity of azobenzenes in visible‐light‐promoted mechanism.

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Photoinduced Ligand‐to‐Metal Charge Transfer of Carboxylates: Decarboxylative Functionalizations, Lactonizations, and Rearrangements
Authors: Gavelle Sigrid , Innocent Milan , Aubineau Thomas , Guérinot Amandine
Published: December 2022

In the quest for sustainable processes, the selection of resources and catalysts is of central importance. Carboxylic acids, which are abundant, stable and ideally biobased feedstocks, can be considered as attractive platforms towards a range of functionalized molecules. A recent resurgence of photoinduced ligand‐to‐metal charge transfer (LMCT) of carboxylates led to tremendous developments in the field of earth‐abundant metal mediated, visible‐light induced (non)‐decarboxylative transformations of carboxylic acids. These reactions combine the use of available starting materials, low‐consuming energy source and abundant catalysts. Besides these undeniable advantages, they also provide mild, highly selective and innovative conditions towards complex molecule functionalization. The objective of this review is to give an overview of the recent advances in LMCT of carboxylates with a special focus on mechanistic aspects of these transformations.

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Review of the Intelligent Sensor‐Memory‐Control Fusion Systems
Authors: Chen Yixuan , Wu Xinyue , Shen Junhao , Huang Zepeng , Wang Zhongrui , Lyu Liangjian , Bi Hengchang , Wu Xing , Shen Guozhen
Published: December 2022

The ability to sense light, heat, and touch is vital for human beings, underpinning the interaction between humans and the environment. To mimic the biological perception system, the sensory system converts external light, heat, and mechanical inputs into electrical signals, then processing and storing the data in digital hardware before providing feedback. However, modern digital sensing‐processing systems based on the von Neumann architecture are facing significant challenges in power consumption and latency due to the unprecedented increase in data size and algorithm complexity. A promising solution is to integrate sensors, memory, and control. Here the “state‐of‐the‐art” fusion systems involved in the sensing of visual, olfactory, tactile, visual signals, and control is reviewed. The challenges in high performance and reliability are also discussed.
Recent Advances in Nanodrug Delivery System for Tumor Combination Treatment Based on Photothermal Therapy
Authors: Qin Jiamin , Wang Xiaoxia , Fan Guojuan , Lv Yanna , Ma Jinlong
Published: December 2022

Although photothermal therapy (PTT) can act on tumors alone, resulting in tumor shrinkage or even eradication, this effect is short‐lived, and the tumor may regrow. Thus, the most helpful contribution of PTT to cancer therapy is to employ it in conjunction with other tumor therapies, such as chemotherapy, immunotherapy, photodynamic therapy, gene therapy, radiotherapy therapy, and multiple combination therapy to boost treatment efficacy. This paper covers the benefits and drawbacks of combining photothermal therapy with various therapeutic approaches by the nanodrug delivery system and the possibilities and obstacles of clinical combination therapy.
Anisotropic Melting Path of Charge‐Ordering Insulator in LSMO/STO Superlattice
Authors: Zhang Bangmin , Yang Ping , Ding Jun , Chen Jingsheng , Chow Gan Moog
Published: December 2022

Multiple phases coexist in manganite with simultaneously active couplings, and the transition among them depends on the relative intensities of different interactions. However, the melting path with variable intensities is unclear. The concentration and the ordering of oxygen vacancy in previous work are found to induce ferromagnetic charge‐ordering insulator phase in [(La0.7Sr0.3MnO3)10/(SrTiO3)5]n superlattice, which translates into metallic phase with magnetic field H and temperature T. In the current work, the H‐T phase diagram for current I//[100] and I//[110] shows a large difference with H normal to the film plane, which is ascribed to the response of a variable range of hopping process to H with the in‐plane anisotropic hopping probability of charge carrier. With H rotating from the out‐of‐plane to the in‐plane direction, the preferred occupancy of the orbital causes a decrease of spin‐orbital coupling and lowers the activation energy, inducing a gentler melting process of a charge‐ordering insulator. This work shows that the melting path of a charge‐ordering insulator phase can be largely modulated in manganite with anisotropy.
Lead‐Free Cesium Manganese Halide Nanocrystals Embedded Glasses for X‐Ray Imaging
Authors: Li Kai , Zhang Wenchao , Niu Luyue , Ye Ying , Ren Jing , Liu Chao
Published: December 2022

The toxicity of heavy‐metal Pb and instability of lead‐based halide perovskite nanomaterials are main factors to impede their practical applications in the fields of solar cells, LEDs and scintillators. In this paper, all inorganic lead‐free cesium manganese halide nanocrystals are synthesized in glass for the first time. Red photoluminescence with broad PL band, negligible self‐absorption and a high photoluminescence quantum yield of 41.8% is obtained. In addition, modulating halide component can change the Mn2+ ions coordination environment to obtain tunable photoluminescence from red to green. More importantly, cesium manganese halide nanocrystals embedded glasses exhibit outstanding long‐term stabilities. Theses cesium manganese halide nanocrystals embedded glasses are also highly stable against high energy irradiation and exhibit highly efficient radioluminescence, making them promising for high‐resolution X‐ray imaging. These results demonstrate that cesium manganese halide nanocrystals embedded glasses are promising eco‐friendly candidates for applications in light‐emitting diodes and scintillators.
A Thermal and Enzymatic Dual‐Stimuli Responsive DNA‐Based Nanomachine for Controlled mRNA Delivery
Authors: Li Feng , Sun Xiaolei , Yang Jing , Ren Jin , Huang Mengxue , Wang Shengqi , Yang Dayong
Published: December 2022

The extreme instability of mRNA makes the practical application of mRNA‐based vaccines heavily rely on efficient delivery system and cold chain transportation. Herein, a DNA‐based nanomachine, which achieves programmed capture, long‐term storage without cryopreservation, and efficient delivery of mRNA in cells, is developed. The polythymidine acid (Poly‐T) functionalized poly(N‐isopropylacrylamide) (DNA‐PNIPAM) is synthesized and assembled as the central compartment of the nanomachine. The DNA‐PNIPAM nano‐assembly exhibits reversible thermal‐responsive dynamic property: when lower than the low critical solution temperature (LCST, ≈32 °C) of PNIPAM, the DNA‐PNIPAM transforms into extension state to expose the poly‐T, facilitating the hybridization with polyadenylic acid (Poly‐A) tail of mRNA; when higher than LCST, DNA‐PNIPAM re‐assembles and achieves an efficient encapsulation of mRNA. It is remarkable that the DNA‐PNIPAM nano‐assembly realizes long‐term storage of mRNA (≈7 days) at 37 °C. Biodegradable 2‐hydroxypropyltrimethyl ammonium chloride chitosan is assembled on the outside of DNA‐PNIPAM to facilitate the endocytosis of mRNA, RNase‐H mediating mRNA release occurs in cytoplasm, and efficient mRNA translation is achieved. This work provides a new disign principle of nanosystem for mRNA delivery.
Dual‐Triggered Near‐Infrared Persistent Luminescence Nanoprobe for Autofluorescence‐Free Imaging‐Guided Precise Therapy of Rheumatoid Arthritis
Authors: Wang Ruoping , Shi Junpeng , Zhang Qian , Peng Qiang , Sun Xia , Song Liang , Zhang Yun
Published: December 2022

Rheumatoid arthritis (RA) is a common, chronic, and highly disabling autoimmune disease characterized by difficult treatment, long disease duration, and easy recurrence. The development and application of high‐sensitivity theranostic probes for RA that will facilitate precise monitoring of disease progression and enable effective treatment are currently hotspots in the field of RA theranostics. In this study, mZMI@HA, a dual‐triggered theranostics nanoprobe, is constructed based on near‐infrared persistent luminescence nanoparticles (NIR‐PLNPs) for precise RA treatment and therapeutic evaluation. This is the first reported use of high‐sensitivity autofluorescence‐free imaging based on NIR‐PLNPs for precise RA treatment and therapeutic evaluation. Compared with the NIR fluorescence imaging probe‐indocyanine green, the signal‐to‐background ratio of persistent luminescence (PersL) imaging is improved nearly 14‐fold. Using PersL imaging to guide photothermal therapy and controllable drug release through NIR/pH‐responsiveness, the progress of collagen‐induced RA is relieved. Additionally, the therapeutic evaluation of RA by PersL imaging is consistent with clinical micro‐computed tomography and histological analyses. This study demonstrates the potential of NIR‐PLNPs for high‐sensitivity imaging‐guided RA treatment, providing a new strategy for RA precise theranostics.
Color‐Tunable and Stable Copper Iodide Cluster Scintillators for Efficient X‐Ray Imaging
Authors: Zhao Wenjing , Wang Yanze , Guo Yuanyuan , Suh Yung Doug , Liu Xiaowang
Published: December 2022

The search for color‐tunable, efficient, and robust scintillators plays a vital role in the development of modern X‐ray radiography. The radioluminescence tuning of copper iodide cluster scintillators in the entire visible region by bandgap engineering is herein reported. The bandgap engineering benefits from the fact that the conduction band minimum and valence band maximum of copper iodide cluster crystals are contributed by atomic orbitals from the inorganic core and organic ligand components, respectively. In addition to high scintillation performance, the as‐prepared crystalline copper iodide cluster solids exhibit remarkable resistance toward both moisture and X‐ray irradiation. These features allow copper iodide cluster scintillators to show particular attractiveness for low‐dose X‐ray radiography with a detection limit of 55  nGy s−1, a value ≈100 times lower than a standard dosage for X‐ray examinations. The results suggest that optimizing both inorganic core and organic ligand for the building blocks of metal halide cluster crystals may provide new opportunities for a new generation of high‐performance scintillation materials.
Organic Phase‐Change Memory Transistor Based on an Organic Semiconductor with Reversible Molecular Conformation Transition
Authors: Hu Yongxu , Zheng Lei , Li Jie , Huang Yinan , Wang Zhongwu , Lu Xueying , Yu Li , Wang Shuguang , Sun Yajing , Ding Shuaishuai , Ji Deyang , Lei Yong , Chen Xiaosong , Li Liqiang , Hu Wenping
Published: December 2022

Phase‐change semiconductor is one of the best candidates for designing nonvolatile memory, but it has never been realized in organic semiconductors until now. Here, a phase‐changeable and high‐mobility organic semiconductor (3,6‐DATT) is first synthesized. Benefiting from the introduction of electrostatic hydrogen bond (S···H), the molecular conformation of 3,6‐DATT crystals can be reversibly modulated by the electric field and ultraviolet irradiation. Through experimental and theoretical verification, the tiny difference in molecular conformation leads to crystalline polymorphisms and dramatically distinct charge transport properties, based on which a high‐performance organic phase‐change memory transistor (OPCMT) is constructed. The OPCMT exhibits a quick programming/erasing rate (about 3 s), long retention time (more than 2 h), and large memory window (i.e., large threshold voltage shift over 30 V). This work presents a new molecule design concept for organic semiconductors with reversible molecular conformation transition and opens a novel avenue for memory devices and other functional applications.
Solid‐State Fluorescent Carbon Dots with Unprecedented Efficiency from Visible to Near‐Infrared Region
Authors: Xu Bin , Li Jie , Zhang Jing , Ning Huiying , Fang Xiaoqi , Shen Jian , Zhou Heng , Jiang Tianlong , Gao Zhenhua , Meng Xiangeng , Wang Zifei
Published: December 2022

Developing solid‐state luminescent materials with bright long‐wavelength emissions is of considerable practical importance in light‐emitting diodes (LEDs) but remains a formidable challenge. Here, a novel structure engineering strategy is reported to realize solid‐state fluorescence (FL)‐emitted carbon dots (CDs) from visible to near‐infrared region. This is the first report of such an extended wavelength emission of self‐quenching‐resistant solid‐state CDs. Notably, the quantum yields of these CDs are remarkably improved up to 67.7%, which is the highest value for solid‐state CDs. The surface polymer chains of CDs can efficiently suppress the conjugated sp2 carbon cores from π–π stacking inducing aggregation caused FL quenching, and the redshift of FL emissions is attributed to narrowing bandgap caused by an enlarged sp2 carbon core. Using these CDs as conversion phosphors, the fabrication of white LEDs with adjustable correlated color temperatures of 1882–5019 K is achieved. Moreover, a plant growth LED device is assembled with a blue‐LED chip and deep‐red/near‐infrared‐emitted CDs. Compared with sunlight and white LEDs, the peanuts irradiated by plant growth LED lamp show higher growth efficiency in terms of branches and leaves. This work provides high‐quality solid‐state CD‐based phosphors for LED lighting sources that are required for diverse optoelectronic applications.
MnAl Layered Double Hydroxides: A Robust Host for Aqueous Ammonium‐Ion Storage with Stable Plateau and High Capacity
Authors: Liu Qiang , Ye Fei , Guan Kailin , Yang Yunting , Dong Hongliang , Wu Yuping , Tang Zilong , Hu Linfeng
Published: December 2022

Rechargeable aqueous batteries based on ammonium‐ions shows great potential in low‐cost energy storage systems owing to their prominent superior characteristics, including ultrafast kinetics, long‐term lifespan, and environmental friendliness. Nevertheless, their development is severely challenged by the fact that the as‐reported cathode materials generally fail to satisfy the requirements on high capacity and stable working voltage simultaneously. Herein, the first NH4+ storage behavior in a MnAl layered double hydroxide (LDH) series is reported. Intriguingly, stable working voltage at 0.2 V is observed in the optimized Mn3Al1‐LDH sample with a high discharge capacity of 183.7 mAh g−1 at 0.1 A g−1. When assembling the rocking‐chair battery using a 3,4,9,10‐perylenetetracarboxylic diimide anode, the full battery delivers a high energy density of 45.8 Wh kg−1, surpassing most of its recently reported counterparts. A rapid amorphization conversion of the LDH cathode during the first charge process is revealed, which should be beneficial to NH4+ isotropic transport accompanied by a highly reversible building/breaking process of hydrogen bonds. The results realize a novel layered inorganic cathode material with superior performance for aqueous ammonium‐ion batteries, and the amorphization conversion to facilitate ion storage provides new insight into electrode design for aqueous batteries.
Na‐Rich Na3V2(PO4)3 Cathodes for Long Cycling Rechargeable Sodium Full Cells
Authors: Liu Yao , Wu Xiangyong , Moeez Abdul , Peng Zhi , Xia Yongyao , Zhao Dongyuan , Liu Jun , Li Wei
Published: December 2022

NASICON‐type sodium vanadium phosphate (Na3V2(PO4)3, or NVP) cathode materials have great potential for fast charging and long cycling sodium‐ion batteries (SIBs) similar to lithium iron phosphate (LiFePO4, or LFP) cathode materials used in lithium‐ion batteries (LIBs). However, the cycle life and energy density in the full cell using NVP materials need to be significantly improved. This paper investigates the degradation mechanisms of NVP‐based SIBs and identifies the Na loss from the cathode to the anode solid electrolyte interphase (SEI) reactions as the main cause of capacity degradation. A new Na‐rich NVP cathode (e.g., Na4V2(PO4)3, or Na4VP) is developed to address the Na loss problem. Conventional NVP can be easily transformed into the Na4VP by a facile and fast chemical solution treatment (30 s). Na‐free‐anode Na4VP and hard carbon‐Na4VP full cells are assembled to evaluate the electrochemical properties of the Na‐rich NVP cathode. The Na4VP cathode provides excess Na to compensate for the Na loss, resulting much longer cycle life in the full cells (>400 cycles) and a high specific energy and power density. Good low‐temperature performance is also observed.
Jack pine of all trades: Deciphering intraspecific variability of a key adaptive trait at the rear edge of a widespread fire‐embracing North American conifer
Authors: Pelletier Emmanuelle , de Lafontaine Guillaume
Published: December 2022

Premise

Understanding mechanisms fostering long‐term persistence of marginal populations should provide key insights about species resilience facing climate change. Cone serotiny is a key adaptive trait in Pinus banksiana (jack pine), which shows phenotypic variation according to the fire regime. Compared to range‐core populations within the fire‐prone boreal forest, low and variable serotiny in rear‐edge populations suggest local adaptation to uncommon and unpredictable wildfire regime. We assessed environmental/physiological factors that might modulate intraspecific variation in cone serotiny.

Methods

We experimentally subjected closed cones to incrementing temperatures, then tested seed germination to determine whether and how various ecological factors (cone age, branch height, tree size, tree age) are related to cone dehiscence and seed viability in jack pines from rear‐edge and range‐core populations in eastern Canada.

Results

Cones from rear‐edge populations dehisce at a lower opening temperature, which increases with cone age. Cones from range‐core stands open at a more constant, yet higher temperature. Cones from rear‐edge stands take between 13 and 27 years to reach the level of serotiny achieved at the range core. At the rear edge, seed viability is steady (51%), whereas it decreases from 70% to 30% in 20 years at the range core.

Conclusions

We inferred the mechanisms of a bet‐hedging strategy in rear‐edge populations, which ensures steady recruitment during fire‐free intervals and successful postfire regeneration. This capacity to cope with infrequent and unpredictable fire regime should increase the resilience of jack pine populations as global changes alter fire dynamics of the boreal forest.
Pollen‐feeding behavior of diverse insects on Geranium delavayi, a flower with large, accessible pollen grains
Authors: Hao Kai , Xu Qi , Huang Shuang‐Quan
Published: December 2022

Premise

Why have pollen grains evolved to be exceptionally large in some species? Pollen‐feeding hypothesis suggests that if the proportion of pollen amounts for feeding is reduced in a flower, the low allocation to pollen number would allow pollen grains to be larger.

Methods

To examine whether species with large pollen grains experience low pollen consumption, the behavior of insects feeding on nectar and pollen was observed and pollen transfer efficiency was estimated for four visitor types in Geranium delavayi. To see whether bees actively collected pollen, the numbers of grains in pollen baskets and on the body were compared. Both nutritional value (total protein and lipid) and chemical defense (phenolic metabolites) in pollen against pollen feeders were measured.

Results

Bumblebees and honeybees foraged for nectar, rarely groomed pollen into corbiculae, and had >5× higher pollen transfer efficiency than smaller solitary bees and flies, which were pollen eaters that removed more pollen but deposited less. Pollen grains were characterized by low protein and high lipid content with a low protein‐lipid ratio, an unfavorable combination for bumblebees. Three secondary metabolites were significantly higher in pollen grains (7.77 mg/g) than in petals (1.08 mg/g) or in nectar (0.44 mg/g), suggesting stronger chemical defense in pollen.

Conclusions

Our results indicated that large bees took nectar but little of the nutritionally poor and highly toxic pollen. These data support one prediction of the pollen‐feeding hypothesis, that species with few and large pollen grains would also have low pollen‐consumption rates.
Climate warming causes photobiont degradation and carbon starvation in a boreal climate sentinel lichen
Authors: Meyer Abigail R. , Valentin Maria , Liulevicius Laima , McDonald Tami R. , Nelsen Matthew P. , Pengra Jean , Smith Robert J. , Stanton Daniel
Published: December 2022

Premise

The long‐term potential for acclimation by lichens to changing climates is poorly known, despite their prominent roles in forested ecosystems. Although often considered “extremophiles,” lichens may not readily acclimate to novel climates well beyond historical norms. In a previous study (Smith et al., 2018), Evernia mesomorpha transplants in a whole‐ecosystem climate change experiment showed drastic mass loss after 1 yr of warming and drying; however, the causes of this mass loss were not addressed.

Methods

We examined the causes of this warming‐induced mass loss by measuring physiological, functional, and reproductive attributes of lichen transplants.

Results

Severe loss of mass and physiological function occurred above +2°C of experimental warming. Loss of algal symbionts (“bleaching”) and turnover in algal community compositions increased with temperature and were the clearest impacts of experimental warming. Enhanced CO2 had no significant physiological or symbiont composition effects. The functional loss of algal photobionts led to significant loss of mass and specific thallus mass (STM), which in turn reduced water‐holding capacity (WHC). Although algal genotypes remained detectable in thalli exposed to higher stress, within‐thallus photobiont communities shifted in composition toward greater diversity.

Conclusions

The strong negative impacts of warming and/or lower humidity on Evernia mesomorpha were driven by a loss of photobiont activity. Analogous to the effects of climate change on corals, the balance of symbiont carbon metabolism in lichens is central to their resilience to changing conditions.
Bone health in RASopathies
Authors: Stevenson David A. , Viscogliosi Germana , Leoni Chiara
Published: December 2022

The RASopathies are a group of disorders due to pathogenic variants in genes involved in the Ras/MAPK pathway, many of which have overlapping clinical features (e.g., neurofibromatosis type 1, Costello syndrome, cardiofaciocutaneous syndrome and Noonan syndrome) including musculoskeletal manifestations. Osteopenia and osteoporosis are reported in many of the RASopathies suggesting a shared pathogenesis. Even though osteopenia and osteoporosis are often detected and fractures have been reported, the clinical impact of bone mineralization defects on the skeleton of the various syndromes is poorly understood. Further knowledge of the role of the Ras/MAPK pathway on the bone cellular function, and more detailed musculoskeletal phenotyping will be critical in helping to develop therapies to improve bone health in the RASopathies.
Mosaic RASopathies: A review of disorders caused by somatic pathogenic variants in the genes of the RAS/MAPK pathway
Authors: Carli Diana , Resta Nicoletta , Ferrero Giovanni Battista , Ruggieri Martino , Mussa Alessandro
Published: December 2022

Mosaic RASopathies are a heterogeneous group of diseases characterized by the presence at birth or early onset of congenital anomalies, cutaneous and vascular anomalies, segmental overgrowth, and increased cancer risk. They are caused by somatic pathogenic variants of the genes belonging the RAt Sarcoma Mitogen‐activated protein kinase (RAS/MAPK) pathway causing its hyperactivation. Here, we review the clinical and molecular characteristics of this heterogeneous group of diseases, including the possibilities of molecular diagnosis and new therapeutic perspectives.
Concurrent hearing and vision impairment and 8‐year memory decline in community‐dwelling older adults
Authors: Huang Alison R. , Rebok George W. , Swenor Bonnielin K. , Reed Nicholas , Griswold Michael , Zhu Xiaoqian , Deal Jennifer A.
Published: December 2022

Background

Hearing and vision impairments are risk factors for cognitive decline; less is known about dual sensory impairment. This study quantifies the association between dual sensory impairment and 8‐year change in memory among older adults.

Methods

Data (N = 5552) were from the National Health and Aging Trends Study. Memory (immediate/delayed word recall, subjective memory) was measured annually (2011 to 2019). Hearing and vision impairments were measured by self‐report. Association between dual sensory impairment and 8‐year change in memory was assessed using multivariate linear mixed effect models and generalized logistic mixed models.

Results

Rate of memory decline was most accelerated among participants with dual sensory impairment. For example, 8‐year decline in delayed word recall was −1.03 (95% confidene interval: ‐1.29, ‐0.77) for dual sensory impairment versus ‐0.79 (‐0.92, ‐0.67) for single and −0.56 (‐0.63, ‐0.48) for no impairment.

Conclusion

Older adults with dual sensory impairment may be at particularly higher risk for cognitive decline.
Amorphous Mo‐doped NiS0.5Se0.5 Nanosheets@Crystalline NiS0.5Se0.5 Nanorods for High Current‐density Electrocatalytic Water Splitting in Neutral Media
Authors: Wang Yang , Li Xiaopeng , Huang Zhong , Wang Haozhi , Chen Zelin , Zhang Jinfeng , Zheng Xuerong , Deng Yida , Hu Wenbin
Published: December 2022

It is vitally important to develop highly active, robust and low‐cost transition metal‐based electrocatalysts for overall water splitting in neutral solution especially at large current density. In this work, amorphous Mo‐doped NiS0.5Se0.5 nanosheets@crystalline NiS0.5Se0.5 nanorods (Am−Mo−NiS0.5Se0.5) was synthesized using a facil one‐step strategy. In phosphate buffer saline solution, the Am−Mo−NiS0.5Se0.5 shows tiny overpotentials of 48 and 209 mV for hydrogen evolution reaction (HER), 238 and 514 mV for oxygen evolution reaction (OER) at 10 and 1000 mA cm−2, respectively. Moreover, Am−Mo−NiS0.5Se0.5 delivers excellent stability for at least 300 h without obvious degradation. Theoretical calculations revealed that the Ni sites in the defect‐rich amorphous structure of Am−Mo−NiS0.5Se0.5 owns higher electron state density and strengthened the binding energy of H2O, which will optimize H adsorption/desorption energy barriers and reduce the adsorption energy of OER determining step.
Potent De Novo Macrocyclic Peptides That Inhibit O‐GlcNAc Transferase through an Allosteric Mechanism
Authors: Alteen Matthew G. , Peacock Hayden , Meek Richard W. , Busmann Jil A. , Zhu Sha , Davies Gideon J. , Suga Hiroaki , Vocadlo David J.
Published: December 2022

Glycosyltransferases are a superfamily of enzymes that are notoriously difficult to inhibit. Here we apply an mRNA display technology integrated with genetic code reprogramming, referred to as the RaPID (random non‐standard peptides integrated discovery) system, to identify macrocyclic peptides with high binding affinities for O‐GlcNAc transferase (OGT). These macrocycles inhibit OGT activity through an allosteric mechanism that is driven by their binding to the tetratricopeptide repeats of OGT. Saturation mutagenesis in a maturation screen using 39 amino acids, including 22 non‐canonical residues, led to an improved unnatural macrocycle that is ≈40 times more potent than the parent compound (Kiapp=1.5 nM). Subsequent derivatization delivered a biotinylated derivative that enabled one‐step affinity purification of OGT from complex samples. The high potency and novel mechanism of action of these OGT ligands should enable new approaches to elucidate the specificity and regulation of OGT.
Tough and Conductive Nacre‐inspired MXene/Epoxy Layered Bulk Nanocomposites
Authors: Wang Huagao , Lu Rongjian , Yan Jia , Peng Jingsong , Tomsia Antoni P. , Liang Rui , Sun Guoxing , Liu Mingjie , Jiang Lei , Cheng Qunfeng
Published: December 2022

A long‐standing quest in materials science has been the development of tough epoxy resin nanocomposites for use in numerous applications. Inspired by nacre, here we report tough and conductive MXene/epoxy layered bulk nanocomposites. The orientation of MXene lamellar scaffolds is enhanced by annealing treatment. The improved interfacial interactions between MXene lamellar scaffold and epoxy through surface chemical modification resulted in a synergistic effect. Tailoring the interlayer spacing of MXene nanosheets to a critical distance resulted in a fracture toughness about eight times higher than that of pure epoxy, surpassing other epoxy nanocomposites. Our nacre‐inspired MXene/epoxy layered bulk nanocomposites also show high electrical conductivity that provides self‐monitoring capability for structural integrity and exhibits an excellent electromagnetic interference shielding efficiency. Our proposed strategy provides an avenue for fabricating high‐performance epoxy nanocomposites.
Giant Tunability of Charge Transport in 2D Inorganic Molecular Crystals by Pressure Engineering
Authors: Feng Xin , Bu Kejun , Liu Teng , Guo Songhao , Sun Zongdong , Fu Tonghuan , Xu Yongshan , Liu Kailang , Yang Sijie , Zhao Yinghe , Li Huiqiao , Lü Xujie , Zhai Tianyou
Published: December 2022

The unique intermolecular van der Waals force in emerging two‐dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α‐Sb2O3 molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α‐Sb2O3 flake shows a sharp drop by 5 orders of magnitude in 0–3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.
Actinorhodin Biosynthesis Terminates with an Unprecedented Biaryl Coupling Reaction
Authors: Hashimoto Makoto , Watari Susumu , Taguchi Takaaki , Ishikawa Kazuki , Kumamoto Takuya , Okamoto Susumu , Ichinose Koji
Published: December 2022

A plethora of dimeric natural products exist with diverse chemical structures and biological activities. A major strategy for dimerization is aryl coupling catalyzed by cytochrome P450 or laccase. Actinorhodin (ACT) from Streptomyces coelicolor A3(2) has a dimeric pyranonaphthoquinone structure connected by a C−C bond. In this study, we identified an NmrA‐family dimerizing enzyme, ActVA‐ORF4, and a cofactor‐independent oxidase, ActVA‐ORF3, both involved in the last step of ACT biosynthesis. ActVA‐ORF4 is a unique NAD(P)H‐dependent enzyme that catalyzes the intermolecular C−C bond formation using 8‐hydroxydihydrokalafungin (DHK‐OH) as the sole substrate. On the other hand, ActVA‐ORF3 was found to be a quinone‐forming enzyme that produces the coupling substrate, DHK‐OH and the final product, ACT. Consequently, the functional assignment of all essential enzymes in the biosynthesis of ACT, one of the best‐known model natural products, has been completed.
Comparison effect of thin microrod‐nanowhisker manganese oxide (MnO2) and spherical grain‐like cobalt oxide (Co3O4) as nanofiller for performance‐enhanced composite gel terpolymer electrolyte‐based dye‐sensitized solar cells
Authors: Razali Ridhwan , Goh Zhi Ling , Farhana Nur Khuzaimah , Kasi Ramesh , Subramaniam Ramesh
Published: December 2022

Gel polymer electrolyte (GPE) are better replacement of liquid electrolyte for dye‐sensitized solar cell (DSSC) but they have low efficiency due to insufficient segmental motion within the electrolyte. By incorporating transition metal oxide nanofiller, it can improve the performance of DSSC due to the existence of cross‐linking center that provides interaction with polymer side chain and redox mediator. Two different transition metal oxides (namely, manganese oxide, MnO2 and cobalt oxide, Co3O4) were synthesized using sonochemical method and incorporated as nanofiller. Poly (vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate) (P(VB‐co‐VA‐co‐VAc)) as a host terpolymer and sodium iodide (NaI) as a dopant salt were used to formulate the composite gel terpolymer electrolytes (CGPEs). The two different shapes of nanofiller have impacted the performance of CGPE proven by the structural analysis. It was found that both systems, the highest ionic conductivity achieved at 2.5 wt% of MnO2 and Co3O4 content with values of 6.40 and 5.2 mS cm−1, respectively. Surprisingly, the performance DSSC of Co3O4‐based CGPE was higher due to the strong Lewis's acidity of Co3O4, which absorb more iodide ions into the surface and facilitating the ions mobility. CGPE containing 2.5 wt% Co3O4 yield the highest efficiency, with value of 3.69%.
Effects of urea loading on soil biodegradation properties of melt‐processed polycaprolactone‐based composites for potential application in agriculture
Authors: Motloung Mpho Phillip , Mofokeng Tladi Gideon , Ray Suprakas Sinha
Published: December 2022

Herein, biodegradable composites of poly(ɛ‐caprolactone) (PCL)/hydroxyapatite (HAP)/urea, with potential application in agriculture, were developed. The concentration of HAP was fixed at 3 wt%, while urea concentration varied from 1 to 9 wt%. The effects of urea loading on the morphological, flow properties, and soil biodegradation of PCL/HAP composites were investigated. The morphological characterization showed well dispersion of HAP and urea particles in the PCL matrix. A decrease in viscosity of PCL was noticed upon the inclusion of urea at 1 wt%, indicating the plasticization effects of urea, whereas an increase in viscosity was observed with increasing the concentration. The morphological analysis after soil burial showed microbial adherence on the surface of the samples. In addition, the formation of cracks, holes, and uneven surfaces were noticed. The atomic force microscope analysis showed an increase in surface roughness due to surface degradation of the samples. On the other hand, two‐step degradation curves were noticed in the samples before soil degradation. In contrast, a single step degradation curve was observed after degradation, indicating the leaching of urea from the samples. Overall, PCL/HAP/urea composites with enhanced degradation rates were developed, and they can be applied in agriculture, where the materials can be buried after their end‐use.
Nanoporous membrane filter cascade for size‐selective analysis of nano‐ and microplastic particles
Authors: Miclea Paul‐Tiberiu , Richter Susanne , Hagendorf Christian
Published: December 2022

Analytical routes for sampling and analysis of microplastic particles in the range of several 10 µm to 1000 µm are well established in environmental research. However, the current scientific efforts are targeting human health impact with an enhanced focus on nanoparticle analysis in drinking water, the food chain, and its disposition in the human body. A major challenge lies in the availability of cascade filter setups spanning several orders of magnitude down to 10 nm dimensions in a single filtration workflow allowing fast and reliable routines for size‐selective nano‐ and microplastic (NMP) particle analysis. In this work, we present a novel cascade filter system containing filters made of microporous Si (pore size >10 µm) and nanoporous Al2O3 (pore size 100 nm), thus realizing the corresponding NMP size selectivity. Inorganic filter materials are chosen due to their beneficial properties as substrates for NMP particle analysis, which are nonpolymer materials with high planarity for micro‐spectroscopy investigations. In our first experiments, we demonstrate the successful NMP size separation on Si and Al2O3 filter substrates. For this purpose, we implement a well‐defined NMP test material composed of a mixture of polyethylene terephthalate microplastic reference material and monodisperse nanoscale polystyrene particles. The NMP test material is applied in a laboratory filtration workflow for samples in liquid solution. Both filter stages are subsequently investigated with optical microscopy, electron microscopy (scanning electron microscopy), Raman spectroscopy, and scanning force microscopy (atomic force microscopy) to demonstrate their applicability as combined NMP particle analytic substrates. Here, we characterize the fundamental NMP properties such as particle shape, size, and spectroscopic fingerprints—optical and chemical—both qualitatively and quantitatively. Finally, requirements and limitations for a standardized NMP filtration and analytic workflow will be discussed.
Synthesis, antimycobacterial, cytotoxicity, anti‐inflammatory, in silico studies and molecular dynamics of pyrazole‐embedded thiazolidin‐4‐one hybrids
Authors: Kamat Vinuta , Poojary Boja , Puthran Divyaraj , Das Vishwa B. , Kumar Banoth K. , Sankaranarayan Murugesan , Shetye Gauri , Ma Rui , Franzblau Scott G. , Nayak Suresh P.
Published: December 2022

In the present investigation, we devolved and synthesized a new series of pyrazole‐embedded thiazolidin‐4‐one derivatives (9a–p) with the goal to produce promising antitubercular leads. The in vitro antimycobacterial activity of the synthesized compounds was tested against replicating and nonreplicating Mtb H37Rv strains. With MIC ranging from 3.03 to 22.55 µg/ml, five compounds (9a, 9c, 9d, 9e, and 9f) emerged as promising antitubercular agents. The active molecules were nontoxic to normal Vero cells. All the synthesized compounds were evaluated for in vitro anti‐inflammatory studies. Compounds 9a, 9b, 9c, 9h, and 9i exhibited excellent anti‐inflammatory efficacy. Docking study was performed to understand the binding pattern of the significantly active compound 9a with 1P44.
Prevalence of nitrosamine contaminants in drug samples: Has the crisis been overcome?
Authors: Schmidtsdorff Sebastian , Neumann Jonas , Schmidt Alexander H. , Parr Maria K.
Published: December 2022

Various drug samples (N = 249; drug substances, tablets, capsules, solutions, crèmes, and more) from the European pharmaceutical market were collected since 2019 and analyzed for 16 nitrosamines (NAs). In 2.0% of the cases, NAs were detected. These findings included four active pharmaceutical ingredients already known for potential NA contamination: losartan (N‐nitrosodimethylamine [NDMA] and N‐nitrosodiethylamine, simultaneously), valsartan (NDMA), metformin (NDMA) and ranitidine (NDMA). The fifth new finding, which has not been reported yet, discovered contamination of a molsidomine tablet sample with N‐nitrosomorpholine (NMor). The tablet contained 144% of the toxicological allowable intake for NMor. NMor was included in our screening from the beginning and is currently the focus of regulatory authorities, but was added to the guidelines only last year. Thus, it may not have been the focus of regulatory investigations for too long. Our results indicate that the majority of drug products in the market are nonhazardous in terms of patient safety and drug purity. Unfortunately, the list of individual affected products keeps growing constantly and new NA cases, such as molsidomine or nitrosated drug substances (nitrosamine drug substance‐related impurities [NDSRI]), continue to emerge. We therefore expect nitrosamine screenings to remain a high priority.