bluuebunny/crossref_metadata_2025 huggingface dataset:
Tuning the Optoelectronic Properties of Pulsed Laser Deposited “3D”‐MoS2 Films via the Degree of Vertical Alignment of Their Constituting Layers
Authors: Mouloua Driss , LeBlanc‐Lavoie Joël , Pichon Loick , Rajput Nitul S , El Marssi Mimoun , Jouiad Mustapha , El Khakani My Ali
Published: March 2024

Pulsed‐laser‐deposition (PLD) is used to deposit MoS2 thin films at substrate temperatures (Td) ranging from 25 to 700 °C. A Td = 500 °C is identified as the optimal temperature that yields MoS2 films consisting of highly‐crystallized 2H‐MoS2 phase with a strong (002) preferential orientation, a direct optical bandgap (Eg) of ∼1.4 eV and a strong photoresponse of ∼1500%. Raman spectroscopy revealed that the degree of vertical alignment of MoS2 layers in the films also reaches its maximum at Td = 500 °C. High‐resolution‐transmission‐electron‐microscopy has provided a clear‐cut evidence that the PLD‐MoS2 films predominantly consist of vertically aligned MoS2 layers over all the film thickness of ∼90 nm, enabling those “3D” films to behave as a direct‐bandgap “2D‐MoS2” with exceptional optoelectronic properties. Indeed, at Td = 500 °C, the PLD‐MoS2 based photodetectors (PDs) devices are shown to exhibit the highest responsivity (R) and detectivity (D*) values (125 mA W−1 and 9.2 × 109 Jones, respectively) ever reported for large area (≥ 1 cm2) MoS2‐based PDs operating at a voltage as low as 1 V. For the first time, a constant‐plus‐linear relationship between Eg, R, and D* of the PDs and the degree of vertical alignment of the MoS2 layers is established. Such a correlation is fundamental for the controlled growth of PLD‐MoS2 films and the tuning of their properties in view of their integration with standard large‐scale‐integration processing.
“Surface‐Filming Assembly” Strategy for Facilely Constructing and Adjusting Circularly Polarized Luminescence from Perovskite/Chiral Helical Polyacetylene Films
Authors: Liu Yanze , Yang Kai , Zhao Biao , Wu Youping , Deng Jianping
Published: March 2024

Tunable circularly polarized luminescence (CPL) has attracted substantial research interest. Till date, the main methods for adjusting CPL is by changing the ratio of fluorescent components and/or regulating external stimuli. Although these adjustment methods have been demonstrated to be reliable, most of them show disadvantages including challenging molecular design, complicated and cumbersome material fabrication, and rigorous adjustment conditions. Herein, the “Surface‐Filming Assembly” (SFA) strategy for conveniently and efficiently modulating CPL by taking the perovskite/chiral helical polyacetylene system as a model is proposed and established. This strategy can facilely achieve multicolor CPL by simply changing the color (or number) of perovskite fluorescent layers and/or the attaching order of the perovskite layers in the assembled multilayer film. Compared with previously reported methods, the SFA strategy integrates the preparation process and adjustment in one single step, simplifying the preparation process (especially the preparation of perovskite with different ratios of halogen atoms) and making adjustment simple and efficient. The SFA strategy and different CPL generation mechanisms to achieve multicolor and white‐color emission with glum up to 10−2 are combined. Based on the CPL film and the solvent sensitivity of perovskite, a solvent‐responsive CPL‐emitting switch and further applied the CPL sample in multiple information displays and encryption are realized.
Abnormal Linear Dichroism in Anisotropic Van der Waals Crystal CrOCl Revealed by Phase‐Dependent Polarized Raman Scattering
Authors: Liu Jinxin , Zheng Miaomiao , Zhang Xiangzhe , Liu Xiao , Luo Shufang , Lin Mingyuan , Luo Wei , Peng Gang , Lv Tieyu , Zhang Xueao , Deng Chuyun
Published: March 2024

Within angle‐resolved polarized Raman spectroscopy (ARPRS) experiments, ensuring accurate configurations is crucial for obtaining reliable results, especially when dealing with anisotropic materials like CrOCl with anisotropic crystal structure and phonon properties. However, comprehensive understanding of phase‐dependent ARPRS and the calibration of phase angle on anisotropic phonon modes from a crystallographic perspective are still lacking. Herein, detailed investigation on phase‐dependent ARPRS and looked into the anisotropic photo‐phonon interaction in CrOCl through in situ ARPRS is conducted. The Raman tensors and crystal orientation are acquired under two typical configurations. Phase‐dependent ARPRS are thoroughly analyzed for the calibration of analyzer deviation. The anomalous anisotropic response in phase‐dependent ARPRS is closely related to the intrinsic linear dichroism (LD) effect in CrOCl, which is further confirmed by angle‐resolved polarization absorption. Moreover, the strong localized rules for various parallel energy bands of CrOCl have generated anomalous LD conversion effect near 470 nm, which expands the potential application of CrOCl in polarization‐wavelength selected devices. This findings can offer in‐depth comprehension on the anisotropic phonon physics of CrOCl and a feasible approach to utilize phase‐dependent ARPRS for probing the undiscovered abundant photo‐induced effects in low‐symmetry 2D materials.
Tunable Circularly Polarized Luminescence by Confining Dye Molecules within Chiral Layered Metal–Organic Framework
Authors: Zhang Shuyu , Huang Jinling , Wang Liping , Li Haitao , Dong Hongyu , Zhu Qi‐Long , Wen Yuehong , Wu Xin‐Tao
Published: March 2024

Circularly polarized luminescence (CPL) active materials have attracted widespread attention because of their potential applications. Nonetheless, it is still a great challenge to fabricate CPL materials with both high fluorescence quantum efficiency (Φ) and high luminescent asymmetry factor (glum). According to the unique structure characteristics of chiral layered metal–organic frameworks (CLMOFs), herein a novel strategy to construct high‐performance CPL materials, by utilizing the confinement effect of CLMOFs is developed. Conjugate dye molecules, such as fluorescent brighteners, fluorescein, and rhodamine B, which are readily subjected to aggregation‐caused quenching (ACQ) effect, are successfully intercalated into CLMOF matrix, affording blue, yellow–green, and red CPL, respectively. Both high Φ and glum values of up to 91% and 0.069 are obtained, owing to the distinct confinement effect of CLMOFs. After confining dye molecules within CLMOF, the ACQ effect is effectively inhibited, which is beneficial for fluorescence enhancement; simultaneously, the chirality transfer from CLMOF matrix to dyes by controlling their arrangement in the chiral confinement microenvironment, leading to the high glum values. Based on the full‐color and strong CPL, a multi‐dimensional code system is proposed. This work paves a new avenue to design and assemble CPL materials with high Φ and glum, which can be widely adopted.
Photothermal Assisted Interfacial Cleaning with Semiconductor‐Based Sorbents: Recent Advances and Future Outlook for Effective Oil Spill Remediation
Authors: Huang Linrong , Liow Jo‐Ey , Lim Kok‐Loong , Tan Kar Woon , Liang Xuan , Khiew Poi Sim , Chiu Wee Siong , Haw Choon‐Yian
Published: March 2024

Oceanic oil spills exert enduring adverse effects on marine ecosystems and human health. In contrast to conventional cleaning methods, advanced oil sorbents present a promising technology characterized by low cost, reduced environmental impact, and exceptional hydrophobicity and oleophilic properties for efficient oil removal from seawater. Despite these advantages, the efficacy of sorbents is hindered by highly viscous oil, impeding the oil/water separation process. To overcome this limitation, solar‐driven sorbents incorporating semiconductor materials are innovatively developed, leveraging increased temperatures to enhance crude oil absorption by reducing viscosity. Herein, a comprehensive review specifically focuses on various semiconductor‐functionalized sorbents for oil spill remediation, elucidating oil weathering and traditional cleaning methods to underscore the complexities and challenges in oil cleaning processes. An in‐depth discussion about the cleaning mechanisms of sorbents and the photothermal conversion processes facilitated by semiconductors is also provided. Additionally, it explores three coupling strategies—Joule heating and solar heating, photothermal effect, and magnetic effect, as well as photothermal and photocatalysis—that offer significant advancements in oil cleanup efficiency. Concluding with forward‐looking insights, the challenges and perspectives for the next generation of ocean oil spill removal technologies are proposed at the end.
Celastrol Ameliorates Neuronal Mitochondrial Dysfunction Induced by Intracerebral Hemorrhage via Targeting cAMP‐Activated Exchange Protein‐1
Authors: Li Xiang , Liu Wen , Jiang Guannan , Lian Jinrong , Zhong Yi , Zhou Jialei , Li Haiying , Xu Xingshun , Liu Yaobo , Cao Cong , Tao Jin , Cheng Jian , Zhang John H , Chen Gang
Published: March 2024

Mitochondrial dysfunction contributes to the development of secondary brain injury (SBI) following intracerebral hemorrhage (ICH) and represents a promising therapeutic target. Celastrol, the primary active component of Tripterygium wilfordii, is a natural product that exhibits mitochondrial and neuronal protection in various cell types. This study aims to investigate the neuroprotective effects of celastrol against ICH‐induced SBI and explore its underlying mechanisms. Celastrol improves neurobehavioral and cognitive abilities in mice with autologous blood‐induced ICH, reduces neuronal death in vivo and in vitro, and promotes mitochondrial function recovery in neurons. Single‐cell nuclear sequencing reveals that the cyclic adenosine monophosphate (cAMP)/cAMP‐activated exchange protein‐1 (EPAC‐1) signaling pathways are impacted by celastrol. Celastrol binds to cNMP (a domain of EPAC‐1) to inhibit its interaction with voltage‐dependent anion‐selective channel protein 1 (VDAC1) and blocks the opening of mitochondrial permeability transition pores. After neuron‐specific knockout of EPAC1, the neuroprotective effects of celastrol are diminished. In summary, this study demonstrates that celastrol, through its interaction with EPAC‐1, ameliorates mitochondrial dysfunction in neurons, thus potentially improving SBI induced by ICH. These findings suggest that targeting EPAC‐1 with celastrol can be a promising therapeutic approach for treating ICH‐induced SBI.
Cascaded p–d Orbital Hybridization Interaction in Ultrathin High‐Entropy Alloy Nanowires Boosts Complete Non‐CO Pathway of Methanol Oxidation Reaction
Authors: Lv Yipin , Liu Pei , Xue Ruixin , Guo Qiudi , Ye Jinyu , Gao Daowei , Jiang Guangce , Zhao Shiju , Xie Lixia , Ren Yunlai , Zhang Pengfang , Wang Yao , Qin Yuchen
Published: March 2024

Designing high efficiency platinum (Pt)‐based catalysts for methanol oxidation reaction (MOR) with high “non‐CO” pathway selectivity is strongly desired and remains a grand challenge. Herein, PtRuNiCoFeGaPbW HEA ultrathin nanowires (HEA‐8 UNWs) are synthesized, featuring unique cascaded p–d orbital hybridization interaction by inducing dual p‐block metals (Ga and Pb). In comparison with Pt/C, HEA‐8 UNWs exhibit 15.0‐ and 4.2‐times promotion of specific and mass activity for MOR. More importantly, electrochemical in situ FITR spectroscopy reveals that the production/adsorption of CO (CO*) intermediate is effectively avoided on HEA‐8 UNWs, leading to the complete “non‐CO” pathway for MOR. Theoretical calculations demonstrate the optimized electronic structure of HEA‐8 UNWs can facilitates a lower energy barrier for the “non‐CO” pathway in the MOR.
“Inverted” Cyclic(Alkyl)(Amino)Carbene (CAAC) Ruthenium Complex Catalyzed Isomerization Metathesis (ISOMET) of Long Chain Olefins to Propylene at Low Ethylene Pressure
Authors: Farkas Vajk , Csókás Dániel , Erdélyi Ádám , Turczel Gábor , Bényei Attila , Nagy Tibor , Kéki Sándor , Pápai Imre , Tuba Róbert
Published: March 2024

Isomerization Metathesis (ISOMET) reaction is an emerging tool for “open loop” chemical recycling of polyethylene to propylene. Novel, latent N‐Alkyl substituted Cyclic(Alkyl)(Amino)Carbene (CAAC)–ruthenium catalysts (5a‐Ru, 3b‐Ru – 6c‐Ru) are developed rendering “inverted” chemical structure while showing enhanced ISOMET activity in combination with (RuHCl)(CO)(PPh3)3 (RuH) double bond isomerization co‐catalyst. Systematic investigations reveal that the steric hindrance of the substituents on nitrogen and carbon atom adjacent to carbene moiety in the CAAC ligand have significantly improved the catalytic activity and robustness. In contrast to the NHC‐Ru and CAAC‐Ru catalyst systems known so far, these systems show higher isomerization metathesis (ISOMET) activity (TON: 7400) on the model compound 1‐octadecene at as low as 3.0 bar optimized pressure, using technical grade (3.0) ethylene. The propylene content formed in the gas phase can reach up to 20% by volume.
Enhancing Interface Connectivity for Multifunctional Magnetic Carbon Aerogels: An In Situ Growth Strategy of Metal‐Organic Frameworks on Cellulose Nanofibrils
Authors: Qiao Jing , Song Qinghua , Zhang Xue , Zhao Shanyu , Liu Jiurong , Nyström Gustav , Zeng Zhihui
Published: March 2024

Improving interface connectivity of magnetic nanoparticles in carbon aerogels is crucial, yet challenging for assembling lightweight, elastic, high‐performance, and multifunctional carbon architectures. Here, an in situ growth strategy to achieve high dispersion of metal–organic frameworks (MOFs)‐anchored cellulose nanofibrils to enhance the interface connection quality is proposed. Followed by a facile freeze‐casting and carbonization treatment, sustainable biomimetic porous carbon aerogels with highly dispersed and closely connected MOF‐derived magnetic nano‐capsules are fabricated. Thanks to the tight interface bonding of nano‐capsule microstructure, these aerogels showcase remarkable mechanical robustness and flexibility, tunable electrical conductivity and magnetization intensity, and excellent electromagnetic wave absorption performance. Achieving a reflection loss of −70.8 dB and a broadened effective absorption bandwidth of 6.0 GHz at a filling fraction of merely 2.2 wt.%, leading to a specific reflection loss of −1450 dB mm−1, surpassing all carbon‐based aerogel absorbers so far reported. Meanwhile, the aerogel manifests high magnetic sensing sensibility and excellent thermal insulation. This work provides an extendable in situ growth strategy for synthesizing MOF‐modified cellulose nanofibril structures, thereby promoting the development of high‐value‐added multifunctional magnetic carbon aerogels for applications in electromagnetic compatibility and protection, thermal management, diversified sensing, Internet of Things devices, and aerospace.
Mimicking Bidirectional Inhibitory Synapse Using a Porous‐Confined Ionic Memristor with Electrolyte/Tris(4‐aminophenyl)amine Neurotransmitter
Authors: Chen Kang , Pan Keyuan , He Shang , Liu Rui , Zhou Zhe , Zhu Duoyi , Liu Zhengdong , He Zixi , Sun Hongchao , Wang Min , Wang Kaili , Tang Minghua , Liu Juqing
Published: March 2024

Ionic memristors can emulate brain‐like functions of biological synapses for neuromorphic technologies. Apart from the widely studied excitatory‐excitatory and excitatory‐inhibitory synapses, reports on memristors with the inhibitory‐inhibitory synaptic behaviors remain a challenge. Here, the first biaxially inhibited artificial synapse is demonstrated, consisting of a solid electrolyte and conjugated microporous polymers bilayer as neurotransmitter, with the former serving as an ion reservoir and the latter acting as a confined transport. Due to the migration, trapping, and de‐trapping of ions within the nanoslits, the device poses inhibitory synaptic plasticity under both positive and negative stimuli. Remarkably, the artificial synapse is able to maintain a low level of stable nonvolatile memory over a long period of time (≈60 min) after multiple stimuli, with feature‐inferencing/‐training capabilities of neural node in neuromorphic computing. This work paves a reliable strategy for constructing nanochannel ionic memristive materials toward fully inhibitory synaptic devices.
Continuous Production of Ethylene and Hydrogen Peroxide from Paired Electrochemical Carbon Dioxide Reduction and Water Oxidation
Authors: Mavrikis Sotirios , Nieuwoudt Matthian , Göltz Maximilian , Ehles Sophie , Körner Andreas , Hutzler Andreas , Fossy Emeric , Zervas Andreas , Brai Oshioriamhe , Wegener Moritz , Doerrfuss Florian , Bouwman Peter , Rosiwal Stefan , Wang Ling , Ponce de León Carlos
Published: March 2024

Paired electrolysis offers an auspicious strategy for the generation of high‐value chemicals, at both the anode and cathode, in an integrated electrochemical reactor. Through efficient electron utilization, routine product misuse at overlooked electrodes can be prevented. Here, an original paired electrosynthetic system is reported that can convert CO2 to ethylene (C2H4) at the cathode, and water to hydrogen peroxide (H2O2) at the anode under a single pass of electric charge. Amongst various investigated copper (Cu) nanomorphologies, the bespoke mixed Cu nanowire/nanoparticle catalyst recorded a peak C2H4 Faraday efficiency (FE) of 60% following 370 h of electrolysis at 200 mA cm−2, while the tailored boron‐doped diamond (BDD) anode accumulated an unprecedented ≈1% w/w of H2O2 in 4 m K2CO3 upon applying 300 mA cm−2 for 10 h. When paired, the dual C2H4‐H2O2 electrochemical cell attains a combined FE of 120% for 50 h at 200 mA cm−2, a combined energy efficiency (EE) of 69%, and a 50% decrease in the overall electrical energy consumption (EEC) compared to the individual electrosynthesis of C2H4 and H2O2.
The effects of agricultural machinery services and land fragmentation on farmers' straw returning behavior
Authors: Wang Xin , Song Yanping , Huang Wei
Published: March 2024

Straw returning is important for rural ecological management and sustainable agricultural development. Using farm survey data for Anhui Province, China, in 2020, we applied the double‐hurdle model to investigate the impact of agricultural machinery services and land fragmentation on farmers' straw‐returning behavior, and to explore the relationship between agricultural machinery self‐service and outsourced service. Self‐service had a significant positive effect on farmers' straw‐returning behavior, while outsourced service had a significant positive effect only on degree of adoption. Land fragmentation had a significant negative effect on farmers' straw‐returning behavior, and significantly inhibited the effect of self‐service on adoption decision. Complementarity existed between self‐service and outsourced service in farmers' straw‐returning adoption decision, and the effect was more pronounced among smaller‐scale farmers. There was significant substitutability between self‐service and outsourced service in degree of adoption among larger‐scale farmers. Transfer and integration of rural land, increasing agricultural machinery purchase subsidy, upgrading farmers' self‐service capability, and promoting development of socialized agricultural machinery services should be implemented to promote crop straw returning. EconLit Citations: Q01, Q16.
Outcomes of laparoscopic and endoscopic cooperative surgery for gastric submucosal tumors: A retrospective multicenter study at 21 Japanese institutions
Authors: Hashimoto Yoshikazu , Abe Nobutsugu , Nunobe Souya , Kawakubo Hirofumi , Sumiyoshi Tetsuya , Yoshida Naohiro , Morita Yoshinori , Terashima Masanori , Saze Zenichiro , Onimaru Manabu , Otsuji Eigo , Hoteya Shu , Yamashita Haruhiro , Fujimura Takashi , Oyama Tsuneo , Ohata Ken , Shichijo Satoki , Tanabe Kazuaki , Shuto Kiyohiko , Ikeya Takashi , Shinohara Hisashi , Tanabe Satoshi , Hiki Naoki
Published: March 2024

Aim

We conducted a multicenter study on classical laparoscopic and endoscopic cooperative surgery (LECS) and LECS‐related procedures to retrospectively clarify the safety, problems, and mid‐term outcomes of these methods after their coverage by the national health insurance.

Methods

A total of 201 patients who underwent classical LECS/LECS‐related procedures for gastric submucosal tumors (G‐SMTs) in 21 institutions affiliated with the Laparoscopy Endoscopy Cooperative Surgery Study Group from April 2014 to March 2016 were included. Data was retrospectively obtained from the patients' charts.

Results

The most common surgical procedure was classical LECS (155 patients, 77.1%), non‐exposed endoscopic wall inversion surgery (22 patients, 11.4%), a combination of laparoscopic and endoscopic approaches to neoplasia with non‐exposure technique (16 patients, 8%), and closed LECS (two patients, 1%). Only six (3%) patients underwent LECS with gastrostomy. The mean operative time and blood loss were 188.4 (70–462) minutes and 23.3 (0–793) g, respectively. Ten (5%) patients developed postoperative complications (Clavien–Dindo classification grade II or higher). Two patients needed reoperation due to postoperative bleeding or anastomotic leakage. All tumors were resected with negative margins. A total of 127 (63.2%) patients underwent follow‐up observations for over 36 months, one of whom had a recurrence of peritoneal dissemination and one had poor oral intake.

Conclusion

Classical LECS and LECS‐related procedures for G‐SMTs have favorable short/mid‐term outcomes.
Origami‐Patterned Rigidification for Soft Robotic Bifurcation
Authors: Liu Dihan , Liu Sicong , Yang Wenjian , Yi Juan , Wang Hongqiang , Zhang Wenzeng , Dai Jian S. , Wang Zheng
Published: March 2024

The fluid‐transportation functions based on the volume‐regulating behavior of the chamber‐like organs inspire the development of artificial organs. Due to the intrinsic compliance of soft robotics for biomimicking purposes and the volume‐regulation capability of the 3D origami patterns, the soft robots with origami patterns show promising potential in such research. However, the folding deformation of the origami facets cannot be straightforwardly implemented as the actuation or the body movement, and the predetermined movements of the pattern limit the appropriate functions for specific applications. In this work, an origami‐patterned rigidification (OPR) method is proposed for applying rigid origami mechanisms (herein, the cuboctahedron origami ball) to the chamber‐like structure of soft robots. The motion of the soft robot is programmed by purposefully rigidified the soft chamber following the pattern. The resultant OPR structures are granted with functions corresponding to the predetermined motion of the pattern, and the expanded movements through the bifurcation brought by the soft–rigid characteristics. The concept, design, and fabrication of the OPR robot are presented. By analyzing the deformation of the soft creases, the kinematic models of the predetermined and expanded degrees of freedom are presented and verified by experiments. The extended functions of two OPR robots are demonstrated.
RNA Control via Redox‐Responsive Acylation
Authors: Guo Junsong , Chen Siqin , Onishi Yoshiyuki , Shi Qi , Song Yangyang , Mei Hui , Chen Leilei , Kool Eric T. , Zhu Ru‐Yi
Published: March 2024

Incorporating stimuli‐responsive components into RNA constructs provides precise spatiotemporal control over RNA structures and functions. Despite considerable advancements, the utilization of redox‐responsive stimuli for the activation of caged RNAs remains scarce. In this context, we present a novel strategy that leverages post‐synthetic acylation coupled with redox‐responsive chemistry to exert control over RNA. To achieve this, we design and synthesize a series of acylating reagents specifically tailored for introducing disulfide‐containing acyl adducts into the 2′‐OH groups of RNA (“cloaking”). Our data reveal that these acyl moieties can be readily appended, effectively blocking RNA catalytic activity and folding. We also demonstrate the traceless release and reactivation of caged RNAs (“uncloaking”) through reducing stimuli. By employing this strategy, RNA exhibits rapid cellular uptake, effective distribution and activation in the cytosol without lysosomal entrapment. We anticipate that our methodology will be accessible to laboratories engaged in RNA biology and holds promise as a versatile platform for RNA‐based applications.
Li3PO4‐Enriched SEI on Graphite Anode Boosts Li+ De‐Solvation Enabling Fast‐Charging and Low‐Temperature Lithium‐Ion Batteries
Authors: Wang Chaonan , Xie Yuansen , Huang Yingshan , Zhou Shaoyun , Xie Huanyu , Jin Hongchang , Ji Hengxing
Published: March 2024

Li+ de‐solvation at solid‐electrolyte interphase (SEI)‐electrolyte interface stands as a pivotal step that imposes limitations on the fast‐charging capability and low‐temperature performance of lithium‐ion batteries (LIBs). Unraveling the contributions of key constituents in the SEI that facilitate Li+ de‐solvation and deciphering their mechanisms, as a design principle for the interfacial structure of anode materials, is still a challenge. Herein, we conducted a systematic exploration of the influence exerted by various inorganic components (Li2CO3, LiF, Li3PO4) found in the SEI on their role in promoting the Li+ de‐solvation. The findings highlight that Li3PO4‐enriched SEI effectively reduces the de‐solvation energy due to its ability to attenuate the Li+‐solvent interaction, thereby expediting the de‐solvation process. Building on this, we engineer Li3PO4 interphase on graphite (LPO−Gr) anode via a simple solid‐phase coating, facilitating the Li+ de‐solvation and building an inorganic‐rich SEI, resulting in accelerated Li+ transport crossing the electrode interfaces and interphases. Full cells using the LPO−Gr anode can replenish its 80 % capacity in 6.5 minutes, while still retaining 70 % of the room temperature capacity even at −20 °C. Our strategy establishes connection between the de‐solvation characteristics of the SEI components and the interfacial structure design of anode materials for high performance LIBs.
Discovery of Terminal Oxazole‐Bearing Natural Products by a Targeted Metabologenomic Approach
Authors: Park Jiyoon , Shin Yern‐Hyerk , Hwang Sunghoon , Kim Jungwoo , Moon Dong Hyun , Kang Ilnam , Ko Yoon‐Joo , Chung Beomkoo , Nam Hyunsung , Kim Seokhee , Moon Kyuho , Oh Ki‐Bong , Cho Jang‐Cheon , Lee Sang Kook , Oh Dong‐Chan
Published: March 2024

A targeted metabologenomic method was developed to selectively discover terminal oxazole‐bearing natural products from bacteria. For this, genes encoding oxazole cyclase, a key enzyme in terminal oxazole biosynthesis, were chosen as the genomic signature to screen bacterial strains that may produce oxazole‐bearing compounds. Sixteen strains were identified from the screening of a bacterial DNA library (1,000 strains) using oxazole cyclase gene‐targeting polymerase chain reaction (PCR) primers. The PCR amplicon sequences were subjected to phylogenetic analysis and classified into nine clades. 1H−13C coupled‐HSQC NMR spectra obtained from the culture extracts of the hit strains enabled the unequivocal detection of the target compounds, including five new oxazole compounds, based on the unique 1JCH values and chemical shifts of oxazole: lenzioxazole (1) possessing an unprecedented cyclopentane, permafroxazole (2) bearing a tetraene conjugated with carboxylic acid, tenebriazine (3) incorporating two modified amino acids, and methyl‐oxazolomycins A and B (4 and 5). Tenebriazine displayed inhibitory activity against pathogenic fungi, whereas methyl‐oxazolomycins A and B (4 and 5) selectively showed anti‐proliferative activity against estrogen receptor‐positive breast cancer cells. This metabologenomic method enables the logical and efficient discovery of new microbial natural products with a target structural motif without the need for isotopic labeling.
Recent Advances in Dearomative Partial Reduction of Benzenoid Arenes
Authors: Liu De‐Hai , Ma Jiajia
Published: March 2024

Dearomative partial reduction is an extraordinary approach for transforming benzenoid arenes and has been well‐known for many decades, as exemplified by the dehydrogenation of Birch reduction and the hydroarylation of Crich addition. Despite its remarkable importance in synthesis, this field has experienced slow progress over the last half‐century. However, a revival has been observed with the recent introduction of electrochemical and photochemical methods. In this Minireview, we summarize the recent advancements in dearomative partial reduction of benzenoid arenes, including dihydrogenation, hydroalkylation, arylation, alkenylation, amination, borylation and others. Further, the intriguing utilization of dearomative partial reduction in the synthesis of natural products is also emphasized. It is anticipated that this Minireview will stimulate further progress in arene dearomative transformations.
Programming of Supercrystals Using Replicable DNA‐Functionalized Colloids
Authors: Sun Xiaoyun , Hua Wenqiang , Liu Xiaoyu , Jin Jing , Zhang Jianing , Tian Jie , Zheng Bin , Jiang Wei , Yao Dongbao , Liang Haojun
Published: March 2024

The development of self‐replicating systems is of great importance in research on the origin of life. As the most iconic molecules, nucleic acids have provided prominent examples of the fabrication of self‐replicating artificial nanostructures. However, it is still challenging to construct sophisticated synthetic systems that can create large‐scale or three‐dimensionally ordered nanomaterials using self‐replicating nanostructures. By integrating a template system containing DNA‐functionalized colloidal seeds with a simplified DNA strand‐displacement circuit programmed subsystem to produce DNA‐functionalized colloidal copies, we developed a facile enthalpy‐mediated strategy to control the replication and catalytic assembly of DNA‐functionalized colloids in a time‐dependent manner. The replication efficiency and crystal quality of the resulting superlattice structures can be effectively increased by regulating the molar ratio of the template to the copy colloids. By constructing binary systems from two types of gold nanoparticles (or proteins), superlattice structures with different crystal symmetries can be obtained through the replication and catalytic assembly processes. This programmable enthalpy‐mediated approach was easily leveraged to achieve the phase transformation and catalytic amplification of colloidal crystals starting from different initial template crystals. This work offers a potential way to construct self‐replicating artificial systems that exhibit complicated phase behaviors and can produce large‐scale superlattice nanomaterials.
6‐Strand to Stable 10/12 Helix Conformational Switch by Incorporating Flexible β‐hGly in the Homooligomers of Camphor Derived β‐Amino Acid: NMR and X‐Ray Crystallographic Evidence
Authors: Sukumar Genji , Rahul  , Nayani Kiranmai , Mainkar Prathama S. , Prashanth Jupally , Sridhar Balasubramanian , Sarma Akella V. S. , Bharatam Jagadeesh , Chandrasekhar Srivari
Published: March 2024

Rational design of unnatural amino acid building blocks capable of stabilizing predictable secondary structures similar to protein fragments is pivotal for foldamer chemistry/catalysis. Here, we introduce novel β‐amino acid building blocks: [1S,2R,4R]exoCDA and [1S,2S,4R]endoCDA, derived from the abundantly available R(+)‐camphor, which is traditionally known for its medicinal value. Further, we demonstrate that the homooligomers of exoCDA adopt 6‐strand conformation, which switches to a robust 10/12‐helix simply by inserting flexible β‐hGly spacer at alternate positions (1 : 1 β‐hGly/exoCDA heterooligomers), as evident by DFT‐calculations, solution‐state NMR spectroscopy and X‐ray crystallography. To the best of our knowledge, this is the first example of crystalline‐state structure of left‐handed 10/12‐mixed helix, that is free from the conventional approach of employing β‐amino acids of either alternate chirality or alternate β2/β3 substitutions, to access the 10/12‐helix. The results also show that the homooligomers of heterochiral exoCDA don′t adopt helical fold, instead exhibit banana‐shaped strands, whereas the homodimers of the other diastereomer endoCDA, nucleate 8‐membered turns. Furthermore, the homo‐exoCDA and hetero‐[β‐hGly‐exoCDA] oligomers are found to exhibit self‐association properties with distinct morphological features. Overall, the results offer new possibilties of constructing discrete stable secondary and tertiary structures based on CDAs, which can accommodate flexible residues with desired side‐chain substitutions.
Sequencing vs. amplification for the estimation of allele dosages in sugarcane (Saccharum spp.)
Authors: Jaimes Hugo , Londoño Alejandra , Saavedra‐Diaz Carolina , Trujillo‐Montenegro Jhon Henry , López‐Gerena Jershon , Riascos John J. , Aguilar Fernando S.
Published: March 2024

Premise

Detecting single‐nucleotide polymorphisms (SNPs) in a cost‐effective way is fundamental in any plant breeding pipeline. Here, we compare three genotyping techniques for their ability to reproduce the allele dosage of SNPs of interest in sugarcane (Saccharum spp.).

Methods

To identify a reproducible technique to estimate allele dosage for the validation of SNP markers, the correlation between Flex‐Seq, kompetitive allele‐specific PCR (KASP), and genotyping‐by‐sequencing and restriction site–associated DNA sequencing (GBS+RADseq) was determined for a set of 76 SNPs. To find alternative methodologies for allele dosage estimation, the KASP and Flex‐Seq techniques were compared for the same set of SNPs. For the three techniques, a population of 53 genotypes from the diverse sugarcane panel of the Centro de Investigación de la Caña de Azúcar (Cenicaña), Colombia, was selected.

Results

The average Pearson correlation coefficients between GBS+RADseq and Flex‐Seq, GBS+RADseq and KASP, and Flex‐Seq and KASP were 0.62 ± 0.27, 0.38 ± 0.27, and 0.38 ± 0.30, respectively.

Discussion

Flex‐Seq reproduced the allele dosages determined using GBS+RADseq with good levels of precision because of its depth of sequencing and ability to target specific positions in the genome. Additionally, Flex‐Seq outperformed KASP by allowing the conversion of a higher number of SNPs and a more accurate estimation of the allele dosage. Flex‐Seq has therefore become the genotyping methodology of choice for marker validation at Cenicaña.
Mixed‐effects regression weights for advice taking and related phenomena of information sampling and utilization
Authors: Rebholz Tobias R. , Biella Marco , Hütter Mandy
Published: March 2024

Advice taking and related research is dominated by deterministic weighting indices, specifically ratio‐of‐differences‐based formulas for investigating informational influence. Their arithmetic is intuitively simple, but they pose several measurement problems and restrict research to a particular paradigmatic approach. As a solution, we propose to specify how strongly peoples' judgments are influenced by externally provided evidence by fitting corresponding mixed‐effects regression models. Our approach explicitly distinguishes between endogenous components, such as updated beliefs, and exogenous components, such as independent initial judgments and advice. Crucially, mixed‐effects regression coefficients of various exogenous sources of information also reflect individual weighting but are based on a conceptually consistent representation of the endogenous judgment process. The formal derivation of the proposed weighting measures is accompanied by a detailed elaboration on their most important technical and statistical subtleties. We use this modeling approach to revisit empirical findings from several paradigms investigating algorithm aversion, sequential collaboration, and advice taking. In summary, we replicate and extend the original finding of algorithm appreciation and initially demonstrate a lack of evidence for both systematic order effects in sequential collaboration as well as differential weighting of multiple pieces of advice. In addition to opening new avenues for innovative research, appropriate modeling of information sampling and utilization has the potential to increase the reproducibility and replicability of behavioral science. Furthermore, the proposed method is relevant beyond advice taking, as mixed‐effects regression weights can also inform research on related cognitive phenomena such as multidimensional belief updating, anchoring effects, hindsight bias, or attitude change.
Rigid linker peptides improve the stability and anti‐inflammation effect of human serum albumin and α‐melanocyte‐stimulating hormone fusion proteins
Authors: Liu Yiyao , Li Yang , Wei Xueyan , Ullah Inam , Uddin Shahab , Wang Jiatao , Xia Runjie , Wang MeiZhu , Yang Hui , Li Hongyu
Published: March 2024

The anti‐inflammatory effect of α‐melanocyte‐stimulating hormone (α‐MSH) in the central nervous system (CNS) has been reported for 40 years. However, the short half‐life of α‐MSH limits its clinical applications. The previous study has shown that a fusion protein comprising protein transduction domain (PTD), human serum albumin (HSA), and α‐MSH extends the half‐life of α‐MSH, but its anti‐inflammatory effect is not satisfactory. In this study, optimization of the structures of fusion proteins was attempted by changing the linker peptide between HSA and α‐MSH. The optimization resulted in the improvement of various important characteristics, especially the stability and anti‐inflammatory bioactivity, which are important features in protein medicines. Compared to the original linker peptide L0, the 5‐amino‐acid rigid linker peptide L6 (PAPAP) is the best option for further investigation due to its higher expression (increased by 6.27%), improved purification recovery (increased by 60.8%), excellent thermal stability (Tm = 83.5°C) and better inhibition in NF‐κB expression (increased by 81.5%). From this study, the significance of the design of linker peptides in the study of structure–activity relationship of fusion proteins was proved.
Enhanced synthesis of S‐adenosyl‐L‐methionine through combinatorial metabolic engineering and Bayesian optimization in Saccharomyces cerevisiae
Authors: Xiao Wenhan , Shi Xiangliu , Huang Haowei , Wang Xiaogang , Liang Wenshu , Xu Jianguo , Liu Fei , Zhang Xiaomei , Xu Guoqiang , Shi Jinsong , Xu Zhenghong
Published: March 2024

S‐Adenosyl‐L‐methionine (SAM) is a substrate for many enzyme‐catalyzed reactions and provides methyl groups in numerous biological methylations, and thus has vast applications in the agriculture and medical field. Saccharomyces cerevisiae has been engineered as a platform with significant potential for producing SAM, but the current production has room for improvement. Thus, a method that consists of a series of metabolic engineering strategies was established in this study. These strategies included enhancing SAM synthesis, increasing ATP supply, down‐regulating SAM metabolism, and down‐regulating competing pathway. After combinatorial metabolic engineering, Bayesian optimization was conducted on the obtained strain C262P6S to optimize the fermentation medium. A final yield of 2972.8 mg·L−1 at 36 h with 29.7% of the L‐Met conversion rate in the shake flask was achieved, which was 26.3 times higher than that of its parent strain and the highest reported production in the shake flask to date. This paper establishes a feasible foundation for the construction of SAM‐producing strains using metabolic engineering strategies and demonstrates the effectiveness of Bayesian optimization in optimizing fermentation medium to enhance the generation of SAM.
Predicting protein retention in ion‐exchange chromatography using an open source QSPR workflow
Authors: Neijenhuis Tim , Le Bussy Olivier , Geldhof Geoffroy , Klijn Marieke E. , Ottens Marcel
Published: March 2024

Protein‐based biopharmaceuticals require high purity before final formulation to ensure product safety, making process development time consuming. Implementation of computational approaches at the initial stages of process development offers a significant reduction in development efforts. By preselecting process conditions, experimental screening can be limited to only a subset. One such computational selection approach is the application of Quantitative Structure Property Relationship (QSPR) models that describe the properties exploited during purification. This work presents a novel open‐source Python tool capable of extracting a range of features from protein 3D models on a local computer allowing total transparency of the calculations. As open‐source tool, it also impacts initial investments in constructing a QSPR workflow for protein property prediction for third parties, making it widely applicable within the field of bioprocess development. The focus of current calculated molecular features is projection onto the protein surface by constructing surface grid representations. Linear regression models were trained with the calculated features to predict chromatographic retention times/volumes. Model validation shows a high accuracy for anion and cation exchange chromatography data (cross‐validated R2 of 0.87 and 0.95). Hence, these models demonstrate the potential of the use of QSPR to accelerate process design.
Recent advances and fundamentals of microalgae cultivation technology
Authors: Rozenberg Julian M. , Sorokin Boris A. , Mukhambetova Amina N. , Emelianova Anna A. , Kuzmin Valentin V. , Belogurova‐Ovchinnikova Oxana Y. , Kuzmin Denis V.
Published: March 2024

Microalgae are considered to be a promising group of organisms for fuel production, waste processing, pharmaceutical applications, and as a source of food components. Unicellular algae are worth being considered because of their capacity to produce comparatively large amounts of lipids, proteins, and vitamins while requiring little room for growth. They can also grow on waste and fix CO2 and nitrogen compounds. However, production costs limit the industrial use of microalgae to the most profitable applications including micronutrient production and fish farming. Therefore, novel microalgae based technologies require an increase of the production efficiencies or values. Here we review the recent studies focused on getting strains with novel characteristics or cultivating techniques that improve production's robustness or efficiency and categorize these findings according to the fundamental factors that determine microalgae growth. Improvements of light and nutrient delivery, as well as other aspects of photobioreactor design, have shown the highest average increase in productivity. Other methods, such as an improvement of phosphorus or CO2 fixation and temperature adaptation have been found to be less effective. Furthermore, interactions with particular bacteria may promote the growth of microalgae, although bacterial and grazer contaminations must be managed to avoid culture failure. The competitiveness of the algal products will increase if these discoveries are applied to industrial settings.
Tuning capsid formation dynamics in recombinant adeno‐associated virus producing synthetic cell lines to enhance full particle productivity
Authors: Lu Min , Lin Yu‐Chieh , Kuo Han‐Jung , Cai Wen , Ye Qian , Zhao Liang , Hu Wei‐Shou
Published: March 2024

Recombinant adeno‐associated virus (rAAV) is widely used as an in vivo delivery vector for gene therapy. It is used in a very large dose, and the large quantities required for broad applications present manufacturing challenges. We have developed a synthetic biology platform of constructing cell lines integrated with essential viral genes which can be induced to produce rAAV without plasmid transfection or virus transduction. Through iterative design‐construct‐characterization cycles, we have showcased the potential of this synthetic cell production system. Systems characterization of the dynamics of viral transcripts and proteins as well as virus assembly and packaging revealed that the expression level and balance of viral genome and capsid protein are keys to not only the productivity but also the full particle content, an important product quality attribute. Boosting cap gene expression by sequential transfection and integration of multiple copies of the cap gene elevated the rAAV titer to levels on a par with traditional plasmid transfection and virus infection. However, overexpression of the cap gene shifted the balance and kinetics of the genome and capsid. We independently tuned the dynamics of genome amplification and capsid protein synthesis by modulating the induction concentration as well as the time profile, and significantly enhanced full particle content while maintaining a high productivity. This strategy of constructing an inducible stable producer cell line is readily adaptable to rAAV vectors of different serotypes and payloads. It can greatly facilitate scalable production of gene therapy vectors.
Marketing plant‐based versus animal‐sourced foods in online grocery stores: A comparative content analysis of sustainability and other product claims in the United States
Authors: Gerber Suzannah , Dix Sadie R. , Cash Sean B.
Published: March 2024

The market share of e‐commerce grocery is swiftly rising, but online product listings may present different environmental sustainability and public health information. We analyzed product marketing content available on retailer websites and product images, comparing plant‐based (PBFs) and animal‐sourced foods (ASFs). Over sixteen thousand marketing and labeling content observations were gathered from seven leading U.S. e‐commerce grocery retailers for top‐selling ASFs and closely‐matched PBFs (N = 134; n = 68 PBFs, n = 66 ASFs), including sustainability, mandatory information, health, sourcing, and hedonic/emotional claims. PBFs averaged 47 total claims, ASFs 28. On‐web claims were substantially higher than on‐pack (PBFs 34 on‐web, 12 on‐pack; ASFs 19 and nine, respectively). On‐web information for the same products varied considerably across retailers, especially for sustainability and mandatory information. PBFs presented mostly sustainability claims on‐pack and health claims on‐web. ASFs led emotional claims and made almost no sustainability claims across settings. Across settings, mandatory information compliance was greater among PBFs whereas ASFs notably lacked disclosures for foods with major allergens. Online grocery lacks standardization—businesses should regard differences as opportunities for marketing sustainable foods.
Multifaceted impact of adipose conditioned media: Obesity‐driven promotion of prostate cancer and cancer stem cell dynamics
Authors: Erdogan Suat , Serttas Riza , Dibirdik Ilker , Turkekul Kader
Published: March 2024

Obesity is an established risk factor for the development and progression of prostate cancer (PC). This study used adipose conditioned media (ACM) from differentiated adipocytes to assess its effect on PC development and aggressiveness. Due to limited research on ACM's impact on isolated PC stem cells (PCSCs), we also examined CD44+ PCSCs. ACM notably boosted interleukin‐1β (IL‐1β), IL‐6, and IL‐8 production in normal prostate epithelial cells and LNCaP cells. It also increased IL‐6 and IL‐8 production in PC3 and CD44+ LNCaP cells, and IL‐1β and IL‐6 production in CD44+ PC3 cells. This indicates that ACM induces the production of inflammatory cytokines in both cancer and prostate epithelial cells. Furthermore, ACM promoted proliferation in androgen receptor (AR)‐negative PC3 cells, CD44+ PC3 PCSCs, and nonmalignant RWPE cells, without affecting AR‐positive LNCaP cells. In addition, ACM‐enhanced invasion and migration potential in both PC3 and CD44+ PC3 cells. Western blot analysis indicated the involvement of NF‐κB and AKT pathways in ACM‐induced proliferation in PC3 cells and NF‐κB in PCSCs. In ACM‐treated PC3 cells, E‐cadherin was downregulated, while N‐cadherin, Snail, vimentin, fibronectin, and Twist were upregulated, suggesting ACM‐induced invasion via classical epithelial‐to‐mesenchymal transition (EMT) pathways. In response to ACM, PCSCs exhibited increased expression of E‐cadherin, Snail, and vimentin, which are partial EMT markers promoting stemness and resistance to apoptosis. In addition, increased expressions of Nanog, Oct3/4, survivin, and Bcl‐2 were observed. Although the molecules we studied have diverse effects on cellular regulation, our data emphasize obesity's multifaceted role in promoting and aggressing PC, notably affecting PCSC populations.