bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tuning Interactions to Control Molecular Down Conversion in [2.2]Paracyclophane Bridged Oligo‐Tetracenes
Authors: Rapp Mario R. , Weiß René , Wollny Anna‐Sophie , Guldi Dirk M. , Bettinger Holger F. 
Published: March 2024

AbstractIn tetracene, the energies of the lowest singlet excited state and twice that of the lowest triplet excited state are similar, allowing both down‐conversion (i.e., singlet fission, SF) and up‐conversion (i.e., triplet‐triplet annihilation up‐conversion, TTA‐UC) processes. Through‐space and through‐bond contributions to the inter‐tetracene coupling in purposefully designed oligomers play a crucial role in determining which of the two processes dominates. In this work, the focus is exclusively on SF in newly synthesized oligo‐tetracenes linked by conjugated [2.2]paracyclophane (PCP) building blocks. By choosing different PCP substitution patterns and by varying the degree of substitution the inter‐tetracene couplings are addressed. An independent variable is connecting the tetracences to the PCP at different positions to alter the through‐bond and through‐space coupling of the resulting oligo‐tetracenes. The novel oligo‐tetracenes are investigated by means of steady‐state and time‐resolved absorption and fluorescence spectroscopies with respect to the initial events of SF, that is, the transformation of a singlet excited state into a correlated triplet pair state. Briefly, through‐space couplings are profoundly weaker than through‐bond couplings that enable the correlated triplet pair state formation. If interactions are through‐space, correlated triplet pair state formation is turned off, while it is turned on if through‐bond interactions are operative.
Oncolytic Virus‐Like Nanoparticles for Tumor‐Specific Gene Delivery
Authors: Li Yuchao , Yang Haiyuan , Zong Xiaoqing , Li Xiaodi , Yuan Pengfei , Yang Caiqi , Chen Xinjie , Yan Xiaodie , Wen Yaoqi , Zhu Tianci , Xue Wei , Dai Jian 
Published: March 2024

AbstractNucleic acid drugs are widely used in biomedical fields. However, one of the main challenges in vivo is to selectively deliver nucleic acid drugs to subcellular compartments. To solve this problem, an oncolytic virus‐like nanoparticle, OV@FN, is constructed that can directly deliver nucleic acids to the cytoplasm through membrane fusion in response to the slightly acidic environment of the tumor. OV@FN is composed of a nano‐core (NA‐Zn@G) that can accurately release nucleic acids in response to high concentrations of glutathione in the cytoplasm of tumor cells and a hybrid membrane vesicle (FN) expressing oncolytic virus fusion membrane glycoprotein (mVSV‐G). The study findings suggest that OV@FN efficiently and selectively delivers nucleic acids to the cytoplasm of tumor cells, as compared to normal cells. Importantly, FN effectively induces tumor cells to form a syncytium, thus promoting intracellular drug diffusion, and enhancing the gene therapy effect. In vivo gene silencing test shows that OVsiR@FN has a significant nucleic acid delivery performance. In the melanoma model, the OV3pdsR@FN shows remarkable tumor ablation ability and improves the immunosuppressive microenvironment of the tumor site. OV@FN offers a novel approach to designing gene delivery and tumor therapy platforms.
A Lithiophilic–Lithiophobic Gradient Solid Electrolyte Interface Toward a Highly Stable Solid‐State Polymer Lithium Metal Batteries
Authors: Zhai Pengfei , Ahmad Niaz , Qu Shuangquan , Feng Ligang , Yang Wen 
Published: March 2024

AbstractThe functional lithiophilic−lithiophobic gradient solid electrolyte interphase (SEI) between Li‐metal anode and solid‐state polymer electrolytes may be effective in addressing the long‐standing issue of side reactions and Li‐dendrite growth during repeated deposition or dissolution in solid‐state polymer‐based high‐energy‐density batteries. Herein, a reliable lithiophilic–lithiophobic gradient SEI (G‐SEI) of LiAg‐LiF/Li3N is in situ formed by AgTFSI, used as an additive for polyethylene oxide‐based electrolyte (PEO‐Ag). The upper layer consists of a lithiophobic LiF/Li3N‐rich layer, wherein LiF possesses a high interfacial energy, while Li3N enables fast Li+ diffusion, which synergistically facilitates the uniform deposition of Li+. Lithiophilic Li–Ag alloy can effectively reduce the nucleation overpotential and promote more planar growth of lithium. Furthermore, such G‐SEI possesses a high mechanical modulus, mitigating the penetration of dendrites through the SEI and thereby preventing the continuous degradation of the PEO‐based electrolyte. As a result, an over three times improvement in the lifespan of Li | PEO‐Ag | LFP cell is achieved, demonstrating an 81.4% capacity retention rate after 500 cycles at 1C, as compared to Li | PEO | LFP cell with common SEI. Thus, the developments of the lithiophilic‐lithiophobic gradient SEI provide a substantial path toward high‐performance solid‐state lithium batteries.
Chemical Vapor Deposition Growth of Atomically Thin SnSb2Te4 Single Crystals Toward Fast Photodetection
Authors: Li Yuan , Li Di , Wazir Nasrullah , Zhu Yong , Wang Yushu , Wang Qiwei , Zhou Wenhan , Zhou Jian , Li Songlin , Li Shaochun , Zhang Shengli , Zeng Haibo , Zhou Wu , Shi Yi , Hao Yufeng 
Published: March 2024

AbstractSnSb2Te4 (SST), a ternary van der Waals (vdW) material, has been widely investigated during last decades for potential applications in superconductivity, thermoelectricity, and optoelectronics. Recently, atomically thin SST has been predicted to show abnormal electronic band structure evolutions, high carrier mobility, and strong light–matter interaction. However, controllable synthesis of such SST crystals has been a huge challenge. Herein, atomically thin SST flakes are prepared via a chemical vapor deposition (CVD) method by using SbCl3, SnCl4·5H2O, and Te as the precursors. Multiple structural characterizations reveal that the SST flakes are single crystals with high crystallinity. Due to the narrow bandgap of 0.42 eV, SST‐based photodetectors have a broadband spectrum detection range from visible light through communication bands (480–1550 nm). More importantly, benefiting from a high room‐temperature carrier mobility over 300 cm2 V−1 s−1, the SST photodetectors demonstrate a response/recovery time of tens of tens of microseconds, which exceeds most typical transition metal dichalcogenide (TMDC) flakes. In addition, the photodetector maintains high performance after being exposed to the air for 2 months, suggesting good environmental stability. These excellent performances suggest that the SST flakes are promising for next‐generation optoelectronics.
Bioinspired Dynamic Matrix Based on Developable Structure of MXene‐Cellulose Nanofibers (CNF) Soft Actuators
Authors: Dai Tiantian , Liu Yanting , Rong Dandan , Wang Meng , Qi Zhenkun , Zhao Yinling , Wang Xiandi , Yang Qing , Wei Lei , Chen Mengxiao 
Published: March 2024

AbstractInspired by natural organisms, soft actuators can convert environmental stimuli into mechanical deformation, making them indispensable for applications in a variety of fields such as soft robotics. MXene, displaying exceptional attributes in conductivity, thermal efficiency, good dispersibility etc., has emerged as a preferred material for high‐performance thermal actuators. However, single actuators struggle to achieve complex tasks realized by intelligent robotic systems. Herein, a bioinspired dynamic matrix is presented utilizing the developable structure of MXene‐cellulose nanofibers (CNF) soft actuators. The inclusion of CNF considerably bolsters the mechanical properties of MXene. The MXene‐CNF film possessed a higher working strain range (≈14%) than pure MXene film (≈2%). The designed developable structures complete the actuating movements. The sensing layer integration with the actuating layer led to an extremely low touch detection limit (0.3 kPa) and expedited actuating‐feedback due to the interaction between contact charging and electrostatic induction. A responsive dynamic matrix containing 3 × 3 soft actuators, completed with a close‐looped sensing‐feedback function, is developed similar to the behavior of the mimosa plant. This mimosa‐inspired dynamic matrix is capable of identifying the source of touch stimuli and providing immediate feedback. This research broadens the potential for enhancing adaptability and intelligence of soft robotic system.
A Coherent Pd–Pd16B3 Core–Shell Electrocatalyst for Controlled Hydrogenation in Nitrogen Reduction Reaction
Authors: Wen Yankun , Wang Tongde , Hao Jiace , Zhuang Zechao , Gao Guohua , Lai Feili , Lu Shuanglong , Wang Xiaofan , Kang Qi , Wu Guangming , Du Mingliang , Zhu Han 
Published: March 2024

AbstractThe manipulation of surface catalytic sites has rarely been explored for metal borides, and the subsurface effects on the electrocatalytic activity of the nitrogen reduction reaction (NRR) remain unknown. Herein, this work develops a core–shell nanoparticle catalyst with a Pd core that ensures high electron transfer rates and an Pd16B3 atomical shell that possess tunable active sites for regulating the NRR. The atomic structural evolution from Pd to Pd16B3 is investigated by precisely controlling the B atom diffusion, molecular rearrangement, and d–sp orbital hybridization. Pd/Pd16B3 core–shell nanocrystals exhibit an exceptional NRR performance with a high NH3 Faradaic efficiency of 30.8%, which is superior to those of pristine Pd (1.2%) and B‐doped Pd (4.8%) under identical conditions, and a yield rate of 0.81 µmol h−1 cm−2. This work discovers that the Pd16B3 shell could promote the NRR selectivity by separating the separating the hydrogen evolution reaction proceeded on hole sites and NRR proceeded on bridge sites, and the Pd core could provide the excellent conductivity to Pd16B3 shell through regulated electron interactions. Consequently, the controlled chemical ordering of palladium boride on palladium surfaces provides insight into the synthesis of advanced NRR electrocatalysts.
Oriented Growth of Parallel‐Standing Bimetallic Nanosheet Arrays for Enhanced Charge Transfer
Authors: Zhou Yu , Hu Yiping , Lu Shaojie , Wang Dong , Ma Dongsheng , Gong Xueqing , Yue Qin 
Published: March 2024

AbstractFabricating highly oriented 2D nanosheet arrays is crucial for boosting their performance in electronics, catalysis, optics, and energy conversion, while it remains a challenge due to the high surface energy often leads to random aggregation or interlaced structure. In this study, it is found that the exposed facet of Fe2O3 can greatly influence the interface growth arrangement of bimetallic hydroxide (NiCo(OH)2) nanosheets. The NiCo(OH)2 nanosheets tend to parallel‐standing on the cubic and spindle Fe2O3 while random‐ and interlaced‐standing on the Fe2O3 hexagonal nanoplates and microspheres. The theoretical simulation further indicates the orientation of deposited hydroxide sheets is decided explicitly by the interfacial lattice match/mismatch. Compared to the common interlaced structure of nanosheets, the parallel‐standing nanosheet arrays reduce grain boundaries and improve the charge transfer efficiency. As a result, the derived NiCoP cages exhibit a promising oxygen evolution reaction performance with an overpotential of 255 mV at 10 mA cm−2, and the maximum current density of 400 mA cm−2 with the overpotential of 319 mV.
Microstructure Optimization in the Shear‐Exfoliated Bi6Cu2Se4O6 through Introducing Reduced Graphene Oxide Leads to Wide‐Ranged Thermoelectric Performance
Authors: Zheng Junqing , Wen Yi , Wang Sining , Li Yichen , Wang Siqi , Zhao Zhe , Liu Shan , Liu Shibo , Gao Xiang , Zhao Li‐Dong 
Published: March 2024

AbstractBi6Cu2Se4O6 is considered as an ideal n‐type thermoelectric material to pair with p‐type BiCuSeO for preparing oxyselenide‐based thermoelectric devices, but its thermoelectric performance is limited by poor electrical conductivity. In this research, the reduced graphene oxide (rGO) nanosheets are introduced into Bi6Cu2Se3.6Cl0.4O6 matrix through liquid‐phase shear exfoliation to modify the microstructure. rGO can insert into matrix grains as intercalations, or embed into grain boundaries as wetting phase, and prompt grain alignment, which contributes to the significantly enhanced carrier mobility, thus leading to an improvement in electrical conductivity from ≈15 S cm−1 to ≈230 S cm−1 at 303 K. Whereafter, the effective donor dopant Nb is chosen to substitute Bi. The carrier concentration is increased without damaging the carrier mobility, resulting in a further improved electrical conductivity of ≈840 S cm−1 at 303 K. Lattice thermal conductivity is also suppressed owing to the intensive phonon scattering by point defects and grain boundaries. Ultimately, a record‐breaking peak ZT ≈0.5 (873 K) and average ZT ≈0.3 (303–873 K) can be achieved in Bi5.91Nb0.09Cu2Se3.6Cl0.4O6 + 0.5% rGO. The microstructure optimization method in this research effectively improves thermoelectric performance, and is anticipated to be applied in other thermoelectrics.
Rational Design of Organic Electrocatalysts for Hydrogen and Oxygen Electrocatalytic Applications
Authors: Cheng Ruiqi , He Xiaoqian , Li Kaiqi , Ran Biao , Zhang Xinlong , Qin Yonghong , He Guanjie , Li Huanxin , Fu Chaopeng 
Published: March 2024

AbstractEfficient electrocatalysts are pivotal for advancing green energy conversion technologies. Organic electrocatalysts, as cost‐effective alternatives to noble‐metal benchmarks, have garnered attention. However, the understanding of the relationships between their properties and electrocatalytic activities remains ambiguous. Plenty of research articles regarding low‐cost organic electrocatalysts started to gain momentum in 2010 and have been flourishing recently though, a review article for both entry‐level and experienced researchers in this field is still lacking. This review underscores the urgent need to elucidate the structure–activity relationship and design suitable electrode structures, leveraging the unique features of organic electrocatalysts like controllability and compatibility for real‐world applications. Organic electrocatalysts are classified into four groups: small molecules, oligomers, polymers, and frameworks, with specific structural and physicochemical properties serving as activity indicators. To unlock the full potential of organic electrocatalysts, five strategies are discussed: integrated structures, surface property modulation, membrane technologies, electrolyte affinity regulation, and addition of anticorrosion species, all aimed at enhancing charge efficiency, mass transfer, and long‐term stability during electrocatalytic reactions. The review offers a comprehensive overview of the current state of organic electrocatalysts and their practical applications, bridging the understanding gap and paving the way for future developments of more efficient green energy conversion technologies.
Deep Learning‐Driven Exploration of Pyrroloquinoline Quinone Neuroprotective Activity in Alzheimer's Disease
Authors: Li Xinuo , Sun Yuan , Zhou Zheng , Li Jinran , Liu Sai , Chen Long , Shi Yiting , Wang Min , Zhu Zheying , Wang Guangji , Lu Qiulun 
Published: March 2024

AbstractAlzheimer's disease (AD) is a pressing concern in neurodegenerative research. To address the challenges in AD drug development, especially those targeting Aβ, this study uses deep learning and a pharmacological approach to elucidate the potential of pyrroloquinoline quinone (PQQ) as a neuroprotective agent for AD. Using deep learning for a comprehensive molecular dataset, blood–brain barrier (BBB) permeability is predicted and the anti‐inflammatory and antioxidative properties of compounds are evaluated. PQQ, identified in the Mediterranean‐DASH intervention for a diet that delays neurodegeneration, shows notable BBB permeability and low toxicity. In vivo tests conducted on an Aβ₁₋₄₂‐induced AD mouse model verify the effectiveness of PQQ in reducing cognitive deficits. PQQ modulates genes vital for synapse and anti‐neuronal death, reduces reactive oxygen species production, and influences the SIRT1 and CREB pathways, suggesting key molecular mechanisms underlying its neuroprotective effects. This study can serve as a basis for future studies on integrating deep learning with pharmacological research and drug discovery.
Modulating Pt‐N/O Bonds on Co‐doped WO3 for Acid Electrocatalytic Hydrogen Evolution with Over 2000 h Operation
Authors: Chen Hengyi , Yu Jidong , Liu Lijia , Gao Rui‐Ting , Gao Zehua , Yang Yang , Chen Zhiqiang , Zhan Sibo , Liu Xianhu , Zhang Xueyuan , Dong Hongliang , Wu Limin , Wang Lei 
Published: March 2024

AbstractDeveloping durable electrocatalysts with high performance for hydrogen evolution reaction (HER) in acid conditions is of prime challenge for hydrogen production. Durability is of important prerequisite for catalyst application. Herein, this work constructs the Co‐doped WO3 loaded with Pt nanoparticles under ammonia treatment (Pt/N‐CoWO3) with the Pt‐N/O‐W interaction, which shows excellent activity and stability for acidic hydrogen production at industrial current density. The electronic structure of Pt species is modulated with enhanced Pt‐N/O bonding by Co doping, hence reinforcing the metal‐support interaction, and greatly enhancing the stability of the catalyst under high current density in acidic media. The resultant Pt/N‐CoWO3 catalyst exhibits the overpotentials of only 94 and 108 mV at high current densities of 1 and 2 A cm−2, respectively. More impressively, Pt/N‐CoWO3 delivers a record operation for acid electrocatalytic hydrogen evolution over 2000 h at 1 A cm−2, denoting its potential for catalyst applications at the industrial current density. This work opens a new avenue for developing Pt‐loading acidic HER catalysts for long‐term operation at ampere‐level current densities in acid conditions.
An Enzymatic Carbon‐Carbon Bond Cleavage and Aldol Reaction Cascade Converts an Angular Scaffold into the Linear Tetracyclic Core of Ochraceopones
Authors: Li Yanqin , Cong Mengjing , Wang Wengui , Zhang Xiufeng , Zhu Yiguang , Song Yongxiang , Zhang Wenjun , Xiao Hua , Liu Yonghong , Zhang Changsheng , Wang Junfeng , Yan Yan 
Published: March 2024

AbstractMeroterpenoids of the ochraceopones family featuring a linear tetracyclic scaffold exhibit exceptional antiviral and anti‐inflammatory activities. The biosynthetic pathway and chemical logic to generate this linear tetracycle, however, remain unknown. In this study, we identified and characterized all biosynthetic enzymes to afford ochraceopones and elucidated the complete biosynthetic pathway. We demonstrated that the linear tetracyclic scaffold of ochraceopones was derived from an angular tetracyclic precursor. A multifunctional cytochrome P450 OchH was validated to catalyze the free‐radical‐initiated carbon‐carbon bond cleavage of the angular tetracycle. Then, a new carbon‐carbon bond was verified to be constructed using a new aldolase OchL, which catalyzes an intramolecular aldol reaction to form the linear tetracycle. This carbon‐carbon bond fragmentation and aldol reaction cascade features an unprecedented strategy for converting a common angular tetracycle to a distinctive linear tetracyclic scaffold in meroterpenoid biosynthesis.
Ethylene trimerization using half‐sandwich titanium‐based catalysts supported on mesoporous silica modified with ionic liquids
Authors: Gharajedaghi Sajjad , Mohamadnia Zahra , Marefat Mohamadreza , Habibi Younes , Ahmadi Ebrahim , Zakavi Saeed 
Published: March 2024

Linear alpha olefins (LAOs) are produced industrially via ethylene oligomerization using catalytic methods. The cost‐effective separation process has sparked significant interest in the selective oligomerization of ethylene to produce alpha‐olefins, including 1‐hexene (1‐C6), in multi‐product commercial processes. In addition, the utilization of immobilized catalysts is crucial because of their reduced environmental impact, ease of catalyst separation, recyclability, and transportability. Furthermore, the use of immobilized catalysts simplifies the purification process, making it easier to isolate pure products. In the present study, mesoporous silica (MS) was first modified with ionic liquids (ILs) consisting BF4− and Br− counter‐anions to prepare IL‐BF4@MS and IL‐Br@MS, respectively. Then 12 catalysts were synthesized through immobilization of the half‐sandwich catalysts with different bridges on the surface of MS, IL‐Br@MS, and IL‐BF4@MS and characterized by BET, TGA, and SEM–EDX‐Mapping analyses. UV–Visible spectroscopy showed a tetrahedral structure for the synthesized complexes. The activity and selectivity of the catalysts for the production of 1‐hexene were studied under specific conditions, including an ethylene pressure of 8 bar, a temperature of 40 °C, and an Al/Ti ratio of 1:2000. The C1‐IL‐BF4@MS immobilized catalyst with cyclohexane middle bridge immobilized on MS modified with IL‐BF4 revealed the highest activity (1199 kg 1‐C6 molTi−1·h−1) at a catalyst concentration of 1.5 μmol. The lowest activity (138 kg 1‐C molTi−1·h−1) was obtained for both C3@MS and C4@MS catalysts.
Design of unknown input integral sliding‐mode discrete observer for linear systems
Authors: Shah Khushboo , Satyanarayana Neeli 
Published: March 2024

AbstractThis paper considers the problem of the observer design to estimate the state and reconstruct the unknown inputs for linear discrete‐time systems in the presence of uncertainties. By appropriate use of system transformation and the integral term in the sliding‐surface design, we propose a novel output injection term in its structure to achieve convergence of the sliding‐manifold. The dimension of the designed observer is independent of the number of additive uncertainties in the model of the plant. A numerical simulation demonstrates the design procedure and compares the proposed observer with the standard proportional integral observer (PIO) design.
Why is end‐of‐life inpatient cost high among cancer patients? A prospective cohort study
Authors: Balasubramanian Ishwarya , Malhotra Chetna ,   the COMPASS study group
Published: March 2024

AbstractBackgroundInpatient cost for cancer patients is high during the last year of life, but reasons for this are not understood. We aim to understand the type of hospital admissions and inpatient services associated with an increase in inpatient cost in last year of life.MethodsWe used survey and billing records of 439 deceased patients with a solid metastatic cancer, enrolled in a prospective cohort study. Based on cost per day of inpatient admissions, we classified admissions as low‐ or high‐intensity. We decomposed the inpatient cost into cost for different inpatient services. We examined the inpatient cost in the last year of life. We also assessed patient characteristics associated with higher inpatient cost in the next 3 months.ResultsTowards death, proportion of inpatient cost for “maintenance care” increased while that for intensive care unit (ICU) and surgeries decreased. Low‐intensity, compared to high‐intensity admissions had a higher proportion of cost for “maintenance care” and a lower proportion for surgeries and ICU. Number of low‐intensity admissions increased more steeply towards death than high‐intensity admissions. Both admission types contributed equally to the share of inpatient cost. Older patients were less likely to have a high‐intensity admission (β:‐0.01, CI: −0.02, 0.00). Greater preference for life extension (β: 0.06, CI: 0.01, 0.11) and inaccurate prognostic belief were associated with higher cost of high‐intensity admissions (β: 0.32, CI: 0.03, 0.62).ConclusionsFindings suggest that inpatient costs in last year of life may be reduced if maintenance care is availed in low‐cost settings such as hospice/palliative care alongside steps to reduce non‐beneficial surgeries and ICU admissions.