bluuebunny/crossref_metadata_2025 huggingface dataset:
Exciton Dissociation into Charge Carriers in Porphyrinic Metal‐Organic Frameworks for Light‐Assisted Li‐O2 Batteries
Authors: Wen Bo , Huang Yaohui , Jiang Zhuoliang , Wang Yuzhe , Hua Weibo , Indris Sylvio , Li Fujun
Published: May 2024

Light‐assisted Li‐O2 batteries exhibit a high round‐trip efficiency attributable to the assistance of light‐generated electrons and holes in oxygen reduction and evolution reactions. Nonetheless, the excitonic effect arising from Coulomb interaction between electrons and holes impedes carrier separation, thus hindering efficient utilization of photo‐energy. Herein, porphyrinic metal‐organic frameworks with (Fe2Ni)O(COO)6 clusters are used as photocathodes to accelerate exciton dissociation into charge carriers for light‐assisted Li‐O2 batteries. The coupling of Ni 3d and Fe 3d orbitals boosts ligand‐to‐metal cluster charge transfer, and hence drives exciton dissociation and activates O2 for superoxide (•O2−) radicals, rather than singlet oxygen (1O2) under photoexcitation. These enable the light‐assisted Li‐O2 batteries with a low total overvoltage of 0.28 V and round‐trip efficiency of 92% under light irradiation of 100 mW cm−2. This work highlights the excitonic effect in photoelectrochemical processes and provides insights into photocathode design for light‐assisted Li‐O2 batteries.
Mechanochemically Robust LiCoO2with Ultrahigh Capacity and Prolonged Cyclability
Authors: Huang Weiyuan , Li Jianyuan , Zhao Qinghe , Li Shunning , Ge Mingyuan , Fang Jianjun , Chen Zhefeng , Yu Lei , Huang Xiaozhou , Zhao Wenguang , Huang Xiaojing , Ren Guoxi , Zhang Nian , He Lunhua , Wen Jianguo , Yang Wanli , Zhang Mingjian , Liu Tongchao , Amine Khalil , Pan Feng
Published: May 2024

Pushing intercalation‐type cathode materials to their theoretical capacity often suffers from fragile Li‐deficient frameworks and severe lattice strain, leading to mechanical failure issues within the crystal structure and fast capacity fading. This is particularly pronounced in layered oxide cathodes because the intrinsic nature of their structures is susceptible to structural degradation with excessive Li extraction, which remains unsolved yet despite attempts involving elemental doping and surface coating strategies. Herein, a mechanochemical strengthening strategy is developed through a gradient disordering structure to address these challenges and push the LiCoO2(LCO) layered cathode approaching the capacity limit (256 mAh g−1, up to 93% of Li utilization). This innovative approach also demonstrates exceptional cyclability and rate capability, as validated in practical Ah‐level pouch full cells, surpassing the current performance benchmarks. Comprehensive characterizations with multiscale X‐ray, electron diffraction, and imaging techniques unveil that the gradient disordering structure notably diminishes the anisotropic lattice strain and exhibits high fatigue resistance, even under extreme delithiation states and harsh operating voltages. Consequently, this designed LCO cathode impedes the growth and propagation of particle cracks, and mitigates irreversible phase transitions. This work sheds light on promising directions toward next‐generation high‐energy‐density battery materials through structural chemistry design.
Laser‐Induced Graphene Toward Flexible Energy Harvesting and Storage Electronics
Authors: Yang Jie , Yu Jiajie , Zhang Ke , Qiao Fen , Yu Gui
Published: May 2024

Energy harvesting and storage devices play an increasingly important role in the field of flexible electronics. Laser‐induced graphene (LIG) with hierarchical porosity, large specific surface area, high electrical conductivity, and mechanical flexibility is an ideal candidate for fabricating flexible energy devices which supply power for other electronic components. Through a simple laser irradiation process with designable routes, abundant precursors (or substrates) rapidly transform into patterned LIG without any other treatments. The structure and physicochemical properties of LIG can be regulated by controlling the processing strategies and parameters, enabling the optimization of device performance. The laser scribing method, as a non‐contact and in situ technique, proves to be efficient in integrating different LIG‐based devices, resulting in all‐in‐one flexible power platforms. Here, a systematic summary of recent advancements in LIG‐based flexible energy electronics is presented. The controllable synthesis of LIG, functional LIG, and 3D architectures are described by elucidating corresponding mechanisms and processing strategies. An overall review of flexible energy conversion and storage devices based on LIG is presented. Eventually, the challenges and opportunities of LIG‐based materials in flexible energy conversion and storage are briefly discussed.
Pencil‐Lead‐Based Quasi‐Equilibrium Glucose Biosensors
Authors: Shachneva Svetlana , Lielpetere Anna , Schuhmann Wolfgang
Published: May 2024

Foreign body response is the main reason for the limited lifetime of implantable glucose biosensors. A new measurement strategy exerting minimal disturbance from the equilibrium glucose concentration in the sensor compartment has been proposed to mitigate its adverse effects on the sensor signal. Here, a new measurement strategy using automatically fabricated and robust pencil‐lead‐based glucose biosensors is implemented. The sensor response depends on critical parameters such as redox‐polymer film thickness, film uniformity, rigidity, polymer composition, and the ratio between the enzyme and the polymer. These parameters are controlled by introducing a short‐chain redox polymer, a low crosslinker amount, a short‐chain electrografting agent and linker, pulse electrografting, and an automated fabrication procedure.
A TaOx/TiOy Bilayer Memristor with Enhanced Synaptic Features for Neuromorphic Computing
Authors: Zhu Mingmin , Yu Zhendi , Hu Gao , Yu Kai , Jiang Yulong , Wang Jiawei , Dong Wenjing , Guo Jinming , Qiu Yang , Yu Guoliang , Zhou Hao‐Miao
Published: May 2024

Memristors are a candidate device for artificial neural systems due to their excellent conductance‐regulation ability and potential to simulate the characteristics of biological synapses. This study fabricated a Pt/TaOx/TiOy/Ti analog artificial synapse memristor that exhibits excellent multilevel storage property with a large on/off ratio of ≈660 times. The dynamic resistive switching mechanism is well expounded and validated by the reset stopping voltage dependent Schottky fitting results. Moreover, the essential biological synaptic characteristics such as long‐term potentiation/depression (LTP/D) and paired‐pulse facilitation (PPF) are successfully mimicked with a low pulse energy consumption of 12.69 nJ. A neuromorphic network constructed on the enhanced symmetry and linearity of conductance for this Pt/TaOx/TiOy/Ti memristive device can achieve 92.45% accuracy in recognizing handwritten pattern. These results demonstrate a significant potential for application Pt/TaOx/TiOy/Ti memristor in non‐volatile memory and bioinspired neuromorphic systems.
Efficient and Ultrastable Iodide Oxidation Reaction Over Defect‐Passivated Perovskite Photoanode for Unassisted Solar Fuel Production
Authors: Yun Juwon , Park Young Sun , Lee Hyungsoo , Jeong Wooyong , Jeong Chang‐Seop , Lee Chan Uk , Lee Jeongyoub , Moon Subin , Kwon Eunji , Lee Soobin , Kim Sumin , Kim Junhwan , Yu Seungho , Moon Jooho
Published: May 2024

Recently, lead halide perovskites have emerged as promising photoanode materials for efficient hydrogen production. However, the sluggish kinetics of the oxygen evolution reaction (OER) and interfacial defect‐mediated charge accumulation inevitably result in efficiency loss and degradation of perovskite photoanodes. Herein, a defect‐passivated electron transport layer‐based perovskite photoanode combined with a catalyst layer favorable is introduced for iodide oxidation reaction bearing a small thermodynamic barrier and rapid kinetics compared to OER for efficient solar fuel generation. The resulting perovskite photoanode revealed a saturated photocurrent density of 22.4 mA cm−2 at 0.3 V versus the reversible hydrogen electrode (VRHE) with an impressive onset potential of −0.2 VRHE as well as durability for 225 h in a neutral electrolyte. In addition, an unbiased hydrogen‐production device comprising a perovskite photoanode and Pt coil electrocatalyst is demonstrated, achieving a remarkable solar‐to‐chemical conversion efficiency of 11.45% and stable operation for 25 h. Moreover, a wireless artificial leaf‐structured device realizing solar‐driven hydrogen generation in natural sea water under outdoor sunlight is presented.
Electrochemical Oxidation of Small Molecules for Energy‐Saving Hydrogen Production
Authors: Sun Hainan , Xu Xiaomin , Fei Liangshuang , Zhou Wei , Shao Zongping
Published: May 2024

Electrochemical water splitting is a promising technique for the production of high‐purity hydrogen. Substituting the slow anodic oxygen evolution reaction with an oxidation reaction that is thermodynamically more favorable enables the energy‐efficient production of hydrogen. Moreover, this approach facilitates the degradation of environmental pollutants and synthesis of value‐added chemicals through the rational selection of small molecules as substrates. Strategies for small‐molecule selection and electrocatalyst design are critical to electrocatalytic performance, with a focus on achieving a high current density, selectivity, Faradaic efficiency, and operational durability. This perspective discusses the key factors required for further advancement, including technoeconomic analysis, new reactor system design, meeting the requirements of industrial applications, bridging the gap between fundamental research and practical applications, and product detection and separation. This perspective aims to advance the development of hybrid water electrolysis applications.
Efficient separation in n‐butyl ether production process from computational thermodynamics to process intensification
Authors: Zhang Yanli , Zhou Mengjin , Wang Yangyang , Zhu Zhaoyou , Wang Yinglong , Cui Peizhe , Qi Jianguang , Yang Jingwei , Wang Fang
Published: May 2024

Biobutanol is a green solvent commonly used as gasoline additive. In this study, it is proposed the separation of azeotropic mixtures of butanol and n‐butyl ether (DBE) using ionic liquids (ILs). Suitable anions [AC]− and [H2PO4]− were screened by COSMO‐RS, and the effect of carbon chain length on the separation effect was investigated using quantum chemical calculations. It was found that the anion was primarily responsible for the separation effect, which grew as the carbon chain grew. Molecular dynamics simulations were used to verify the separation performance of the selected ILs. The separation effect of ILs was further verified using vapor–liquid phase equilibrium (VLE) experiments. The extractive distillation process with [PrMIM][AC] as the extractant was investigated to demonstrate the feasibility of ILs for the separation of butanol and DBE. This study analyzes the whole process from microscopic mechanism of action, which provides new ideas for the separation of alcohol‐ether systems.
Biobutanol extraction and dehydration with eucalyptus oil yielding linear and cyclic biofuel blends
Authors: Tan Jialin , Huang Hao , Li Hengde , Cai Xiaolan , Zhou Guangping , Zeng Boxi , He Jinrui , Wang Xiang , Xie Shaoqu
Published: May 2024

The biobutanol‐based biofuel fermentation is hindered by the challenge of inadequate fermentation broth concentration and the azeotropic systems of water. The application of eucalyptus oil in diesel fuel makes it a promising extractant for biobutanol extraction and dehydration, thus resulting in product recovery and the development of fuel blend technology. Eucalyptus oil‐derived 1,8‐cineole was applied to acetone‐butanol‐ethanol (ABE) and isobutanol systems to enhance the butanol recovery and dehydration. The recovery of n‐butanol and isobutanol reached 92% and 95%, respectively, while the water removal in a 2% butanol system exceeded 99%. These results demonstrated that 1,8‐cineole exhibited a high selectivity toward butanol, thus providing a robust theoretical foundation for the fermentation‐based biofuel recovery and the elimination of azeotropic systems. The introduction of high‐density diesel‐fuel‐like eucalyptus oil into low‐energy‐density biobutanol will increase the energy density of fermentation‐based alcohols, yielding linear and cyclic biofuel blends.
SUGP2 p.(Arg639Gln) variant is involved in the pathogenesis of hemochromatosis via the CIRBP/BMPER signaling pathway
Authors: Li Yanmeng , Xu Anjian , Liu Susu , Zhang Wei , Zhou Donghu , OuYang Qin , Zi Huaduan , Zhang Bei , Zhang Ning , Geng Wei , Zhou Yiming , Duan Weijia , Wang Xiaoming , Zhao Xinyan , Ou Xiaojuan , Fan Changfa , Jia Jidong , Huang Jian
Published: May 2024

Pathogenic variants in HFE and non‐HFE genes have been identified in hemochromatosis in different patient populations, but there are still a certain number of patients with unexplained primary iron overload. We recently identified in Chinese patients a recurrent p.(Arg639Gln) variant in SURP and G‐patch domain containing 2 (SUGP2), a potential mRNA splicing‐related factor. However, the target gene of SUGP2 and affected iron‐regulating pathway remains unknown. We aimed to investigate the pathogenicity and underlying mechanism of this variant in hemochromatosis. RNA‐seq analysis revealed that SUGP2 knockdown caused abnormal alternative splicing of CIRBP pre‐mRNA, resulting in an increased normal splicing form of CIRBP V1, which in turn increased the expression of BMPER by enhancing its mRNA stability and translation. Furthermore, RNA‐protein pull‐down and RNA immunoprecipitation assays revealed that SUGP2 inhibited splicing of CIRBP pre‐mRNA by a splice site variant at CIRBP c.492 and was more susceptible to CIRBP c.492 C/C genotype. Cells transfected with SUGP2 p.(Arg639Gln) vector showed up‐regulation of CIRBP V1 and BMPER expression and down‐regulation of pSMAD1/5 and HAMP expression. CRISPR‐Cas9 mediated SUGP2 p.(Arg622Gln) knock‐in mice showed increased iron accumulation in the liver, higher total serum iron, and decreased serum hepcidin level. A total of 10 of 54 patients with hemochromatosis (18.5%) harbored the SUGP2 p.(Arg639Gln) variant and carried CIRBP c.492 C/C genotype, and had increased BMPER expression in the liver. Altogether, the SUGP2 p.(Arg639Gln) variant down‐regulates hepcidin expression through the SUGP2/CIRBP/BMPER axis, which may represent a novel pathogenic factor for hemochromatosis.
A Coppoborylene Stabilized by Multicenter Covalent Bonding and Its Amphoteric Reactivity to CO
Authors: Hu Jin , Xing Xiaopeng , Wang Xuefeng
Published: May 2024

A cationic copper‐stabilized coppoborylene was prepared and structurally characterized via infrared photodissociation spectroscopy and density functional theory calculations. This structure exemplifies a new class of borylenes stabilized by three‐center‐two‐electron metal‐boron‐metal covalent bonding interaction, displaying exceptional σ‐acidity and unparalleled π‐donor capability for CO activation that outperforms all of the known transition metal cations and is comparable or even superior to the documented base‐trapped borylenes. Its neutral form represents a monovalent boron compound with a strongly reactive amphoteric boron center built on transition‐metal‐boron bonds, which inspires the design and synthesis of new members of the borylene family.
Chiral Tetrakis Eu(III) Complexes with Ammonium Cations for Improved Circularly Polarized Luminescence
Authors: Tsurui Makoto , Takizawa Ryohei , Kitagawa Yuichi , Wang Mengfei , Kobayashi Masato , Taketsugu Tetsuya , Hasegawa Yasuchika
Published: May 2024

Large dissymmetry factor of the circularly polarized luminescence (gCPL) was observed in ligand and coordination tuned chiral tetrakis europium (Eu(III)) complexes with ammonium cations. The gCPL value was estimated to be −1.54, which is the largest among chiral luminescent molecules. Through photophysical measurements, single crystal X‐ray structural analyses and quantum chemical calculations, changes in the geometric and electronic structures were observed for a series of chiral tetrakis Eu(III) complexes which enhanced the gCPL value. The emission quantum yield and photosensitized energy transfer efficiencies of chiral Eu(III) complexes with ammonium cations were also larger than those of chiral Eu(III) complex with Cs+. Based on the systematic modifications and analyses for chiral tetrakis Eu(III) complex, effect of the ammonium cation on enhanced CPL brightness is reported.
Exfoliatable Layered 2D Honeycomb Crystals of Host‐guest Complexes Networked by CH‐π Hydrogen Bonds
Authors: Terasaki Seiya , Kotani Yuki , Katsuno Ryosuke , Matsuno Taisuke , Fukunaga Toshiya M. , Ikemoto Koki , Isobe Hiroyuki
Published: May 2024

Studies of graphene show that robust chemical bonds such as covalent bonds with trigonal‐planar atoms afford layered atomic 2D crystals possessing unique properties. Although layered molecular crystals are of interest to diversify elements and structures of 2D materials, the structural diversity of molecules as well as weak intermolecular interactions inevitably makes the design to be one‐off and individual. We herein report a versatile method to assemble layered molecular crystals. By developing a D3‐symmetry host at vertices to form a honeycomb layer, a diverse range of layered 2D host–guest crystals were obtained. Substituents on the host, elements/structures of the guest, the stereochemistry of the host and types of intercalants were diversified, which should allow for 6×32×3×2 combinations for structural diversification.
A Merger of Relay Catalysis with Dynamic Kinetic Resolution Enables Enantioselective β‐C(sp3)−H Arylation of Alcohols
Authors: Lainer Bruno , Li Shuailong , Mammadova Flora , Dydio Paweł
Published: May 2024

The conceptual merger of relay catalysis with dynamic kinetic resolution strategy is reported to enable regio‐ and enantioselective C(sp3)‐H bond arylation of aliphatic alcohols, forming enantioenriched β‐aryl alcohols typically with >90 : 10 enantiomeric ratios (up to 98 : 2 er) and 36–74 % yields. The starting materials bearing neighbouring stereogenic centres can be converted to either diastereomer of the β‐aryl alcohol products, with >85 : 15 diastereomeric ratios determined by the catalysts. The reactions occur under mild conditions, ensuring broad compatibility, and involve readily available aryl bromides, an inorganic base, and commercial Ru‐ and Pd‐complexes. Mechanistic experiments support the envisioned mechanism of the transformation occurring through a network of regio‐ and stereoselective processes operated by a coherent Ru/Pd‐dual catalytic system.
Sulfonated poly (ether ether ketone)/MOF hybrid polymer electrolyte membrane with ultra‐low methanol permeability for enhanced direct methanol fuel cell performance
Authors: Divya Kumar , Liu Huiyuan , Zhang Weiqi , Xu Qian , Su Huaneng
Published: May 2024

A novel hybrid polymer electrolyte membrane (PEM) was developed for direct methanol fuel cell (DMFC) applications by incorporating sulfonated poly (ether ether ketone) (SPEEK) with a chromium‐based metal–organic framework (MOF), namely, BUT‐8(Cr). The incorporation of BUT‐8(Cr) significantly improved the dispersion of the MOF within the SPEEK matrix, leading to alterations in surface morphology and the creation of hydrophilic channels, as confirmed by SEM. Furthermore, the presence of an excess of sulfonic groups and the flexible structure of the MOF enhanced the physicochemical properties of the membrane, such as water uptake, proton conductivity and ion exchange capacity. Importantly, well‐defined rigid coordination structure of MOF effectively blocks methanol migration, resulting in a notably low methanol permeability value of 1.6 × 10−7 cm2 s−1, compared to Nafion 117 (20 × 10−7cm2s−1). For practical DMFC operation, the hybrid membrane (~0.75 wt.% MOF) exhibited a maximum power density of 88.6mWcm−2 with current density of 434.04 mAcm−2, outperforming Nafion 117 (73.4mWcm−2 and 380 mAcm−2 respectively) at same conditions. Our results suggest that the prepared SPEEK‐0.75 hybrid membrane holds a great promise as a PEM material for DMFC applications.
Zinc Tetrafluoroborate Catalyzed Stereo‐ and Regioselective O‐Glycosylation for the Direct Synthesis of β‐Glycosides from Armed O‐Glycosyl Trichloroacetimidates
Authors: Manash Bharali Mrinmoy , Pramanik Swapnendu , Santra Abhishek
Published: May 2024

Efficient stereo‐ and regioselective O‐glycosylation methods remain essential to capacitate the studies of sugars and sugar derivatives in various disciplines. In this work, we demonstrated an operationally simple and cost‐effective strategy for the synthesis of 1,2‐trans glycosides by the activation of armed O‐glycosyl trichloroacetimidates donor using zinc tetrafluoroborate. This mild, transition metal‐free, and scalable approach allowed stereo‐ and regioselective synthesis of β‐glycosides with a wide range of acceptors containing various protecting groups/functionalities. This method is exemplified by synthesizing a branched trisaccharide fragment related to the cell wall O‐polysaccharide of E. Coli O27.
Absent or hypoplastic nasal bone: What to tell the prospective parents?
Authors: Das Shreya , Sharma Charu , Yadav Taruna , Dubey Kalika , Shekhar Shashank , Singh Pratibha , Singh Kuldeep , Gothwal Meenakshi , Jhirwal Manisha , Shekhawat Dolat Singh
Published: May 2024

Background

Absent or hypoplastic nasal bone (AHNB) on first or second‐trimester ultrasonography (USG) is an important soft marker of Down syndrome. However, due to its varied incidence in euploid and aneuploid fetuses, there is always a dilemma of whether to go for invasive fetal testing for isolated AHNB. This study aims to assess outcomes specifically within the context of Indian ethnicity women.

Materials and Methods

This was a prospective observational study. All patients who reported with AHNB in the first‐ or second‐trimester USG were included. Genetic counseling was done, and noninvasive and invasive testing was offered. Chromosomal anomalies were meticulously recorded, and pregnancy was monitored.

Results

The incidence of AHNB in our study was 1.16% (47/4051). Out of 47 women with AHNB, the isolated condition was seen in 32 (0.78%) cases, while AHNB with structural anomalies was seen in nine cases (0.22%). Thirty‐nine women opted for invasive testing. Six out of 47 had aneuploidy (12.7%), while two euploid cases (4.25%) developed nonimmune hydrops. The prevalence of Down syndrome in fetuses with AHNB was 8.5% (4/47) and 0.42% (17/4004) in fetuses with nasal bone present. This difference was statistically significant (p = .001).

Conclusion

The results indicate that isolated AHNB cases should be followed by a comprehensive anomaly scan rather than immediately recommending invasive testing. However, invasive testing is required when AHNB is associated with other soft markers or abnormalities. As chromosomal microarray is more sensitive than standard karyotype in detecting chromosomal aberrations, it should be chosen over karyotype.
Dauerhafter und nachhaltiger Korrosionsschutz des Betonstahls in Verkehrswasserbauwerken
Authors: Rahimi Amir , Westendarp Andreas
Published: May 2024

Korrosionsschäden aufgrund bislang wenig bekannter Schädigungsmechanismen, die kritische Reflexion bisheriger Planungsgrundsätze, aber auch neue baustoffliche Entwicklungen geben Anlass zu einer Neuorientierung bei der Planung von Maßnahmen zur Sicherstellung der Dauerhaftigkeit von Verkehrswasserbauwerken hinsichtlich Betonstahlkorrosion.
Development and application of an RNA nanostructure to induce transient RNAi in difficult transgenic plants
Authors: Zhao Xiayang , Liu Zhekai , Liu Yiqing , Lu Mingdong , Xu Jinfeng , Wu Fangli , Jin Weibo
Published: May 2024

The development of RNA interference (RNAi) is crucial for studying plant gene function. Its use, is limited to a few plants with well‐established transgenic techniques. Spray‐induced gene silencing (SIGS) introduces exogenous double‐stranded RNA (dsRNA) into plants by spraying, injection, or irrigation, triggering the RNAi pathway to instantly silence target genes. As is a transient RNAi technology that does not rely on transgenic methods, SIGS has significant potential for studying gene function in plants lacking advanced transgenic technology. In this study, to enhance their stability and delivery efficiency, siRNAs were used as structural motifs to construct RNA nanoparticles (NPs) of four shapes: triangle, square, pentagon, and hexagon. These NPs, when synthesized by Escherichia coli, showed that triangular and square shapes accumulated more efficiently than pentagon and hexagon shapes. Bioassays revealed that RNA squares had the highest RNAi efficiency, followed by RNA triangles, with GFP‐dsRNA showing the lowest efficiency at 4 and 7 days post‐spray. We further explored the use of RNA squares in inducing transient RNAi in plants that are difficult to transform genetically. The results indicated that Panax notoginseng‐derived MYB2 (PnMYB2) and Camellia oleifera‐derived GUT (CoGUT) were significantly suppressed in P. notoginseng and C. oleifera, respectively, following the application of PnMYB2‐ and CoGUT‐specific RNA squares. These findings suggest that RNA squares are highly effective in SIGS and can be utilized for gene function research in plants.
High‐activity recombinant human carboxypeptidase B expression in Pichia pastoris through rational protein engineering and enhancing secretion from the Golgi apparatus to the plasma membrane
Authors: Li Jia , Shao Qinan , Xiang Yulong , Li Jianghua , Chen Jian , Du Guocheng , Kang Zhen , Wang Yang
Published: May 2024

Human carboxypeptidase B1 (hCPB1) is vital for recombinant insulin production, holding substantial value in the pharmaceutical industry. Current challenges include limited hCPB1 enzyme activity. In this study, recombinant hCPB1 efficient expression in Pichia pastoris was achieved. To enhance hCPB1 secretion, we conducted signal peptides screening and deleted the Vps10 sortilin domain, reducing vacuolar mis‐sorting. Overexpression of Sec4p increased the fusion of secretory vesicles with the plasma membrane and improved hCPB1 secretion by 20%. Rational protein engineering generated twenty‐two single‐mutation mutants and identified the A178L mutation resulted in a 30% increase in hCPB1 specific activity. However, all combinational mutations that increased specific activities decreased protein expression levels. Therefore, computer‐aided global protein design with PROSS was employed for the aim of improving specific activities and preserving good protein expression. Among the six designed mutants, hCPB1‐P6 showed a remarkable 114% increase in the catalytic rate constant (kcat), a 137% decrease in the Michaelis constant (Km), and a 490% increase in catalytic efficiency. Most mutations occurred on the surface of hCPB1‐P6, with eight sites mutated to proline. In a 5 L fermenter, hCPB1‐P6 was produced by the secretion‐enhanced P. pastoris chassis to 199.6 ± 20 mg L−1 with a specific activity of 96 ± 0.32 U mg−1, resulting in a total enzyme activity of 19137 ± 1131 U L−1, demonstrating significant potential for industrial applications.
A LC–MS/MS method for the simultaneous determination of 6‐cyanodopamine, 6‐nitrodopamine, 6‐nitrodopa, 6‐nitroadrenaline and 6‐bromodopamine in human plasma and its clinical application in patients with chronic kidney disease
Authors: Ribeiro Luiz Fernando , Babadopulos Tainah , de Oliveira Mariana G. , Nishimaru Flávio , Zatz Roberto , Elias Rosilene Motta , Moraes Odorico , Moraes Elisabete , Peterson Larryn W. , De Nucci Gilberto
Published: May 2024

The aim of this study was to develop a high‐performance liquid chromatography–tandem mass spectrometry method for the determination of 6‐cyanodopamine, 6‐nitrodopamine, 6‐nitrodopa, 6‐nitroadrenaline and 6‐bromodopamine in human plasma samples. Strata‐X 33 μm solid‐phase extraction cartridges were used for the extraction of the catecholamines from human plasma samples. The catecholamines were separated in a 150 × 3 mm Shim‐pack GIST C18‐AQ column with 3 μm particle size, placed in an oven at 40°C and perfused with 82% mobile phase A (acetonitrile–H2O; 90:10, v/v) + 0.4% acetic acid and 18% mobile phase B (deionized H2O) + 0.2% formic acid at a flow rate of 340 μl/min in isocratic mode. The injected volume was 4 μl and the run lasted 4 min. The method was linear from 0.1 to 20 ng/ml and the lower limit of quantification was 0.1 ng/ml for all analytes. The method was applied to evaluate the plasma levels of catecholamines in plasma of patients with chronic kidney disease and allowed the detection for the first time of circulating levels of the novel catecholamines 6‐bromodopamine and 6‐cyanodopamine.
A radiomics‐based nomogram may be useful for predicting telomerase reverse transcriptase promoter mutation status in adult glioblastoma
Authors: Li Yao , Chen Ling , Huang Lizhao , Li Xuedong , Huang Qidan , Tang Lifang , Huang Zhiwei , Zhu Li , Li Tao
Published: May 2024

Background and purpose

As a crucial diagnostic and prognostic biomarker, telomerase reverse transcriptase (TERT) promoter mutation holds immense significance for personalized treatment of patients with glioblastoma (GBM). In this study, we developed a radiomics nomogram to determine the TERT promoter mutation status and assessed its prognostic efficacy in GBM patients.

Methods

The study retrospectively included 145 GBM patients. A comprehensive set of 3736 radiomics features was extracted from preoperative magnetic resonance imaging, including T2‐weighted imaging, T1‐weighted imaging (T1WI), contrast‐enhanced T1WI, and fluid‐attenuated inversion recovery. The construction of the radiomics model was based on integrating the radiomics signature (rad‐score)with clinical features. Receiver‐operating characteristic curve analysis was employed to evaluate the discriminative ability of the prediction model, and the risk score was used to stratify patient outcomes.

Results

The least absolute shrinkage and selection operator classifier identified 10 robust features for constructing the prediction model, and the radiomics nomogram exhibited excellent performance in predicting TERT promoter mutation status, with area under the curve values of.906 (95% confidence interval [CI]:.850–.963) and.899 (95% CI:.708–.966) in the training and validation sets, respectively. The clinical utility of the radiomics nomogram is further supported by calibration curve and decision curve analyses. Additionally, the radiomics nomogram effectively stratified GBM patients with significantly different prognoses (HR = 1.767, p = .019).

Conclusion

The radiomics nomogram holds promise as a modality for evaluating TERT promoter mutations and prognostic outcomes in patients with GBM.
Comparing child and adult sexual homicides in Australia and New Zealand: A retrospective study
Authors: Ricono‐Kaufhold Sophia , Czarnietzki Marie , Darjee Rajan , Brooks Nathan , Nanev Aleshia , Davis Michael R.
Published: May 2024

The present study examined distinctions between child (n = 30) and adult (n = 212) sexual homicide offenders (SHOs) in Australia and New Zealand, contributing to the limited international research on the subject. Data, primarily sourced from judges' sentencing comments on AustLII and New Zealand Legal Information Institute, revealed significant differences. Child SHOs displayed elevated rates of pedophilia, sexual deviance, and adverse childhood experiences, including sexual abuse. They were more likely to be married, cohabitate, and target familial victims. Their crimes were more often committed during daylight and outdoors, involving tactics such as victim conning, restraints, strangulation, and hiding victim's bodies. No significant group differences emerged regarding offenders' psychopathy or sexual sadism scores. Results were interpreted in line with child SHOs' deviant sexual preferences and the routine activity theory. The study, as the first investigating child sexual homicides in Australia and New Zealand, sets the foundation for an evidence‐based approach to policy and practice.
Propionate‐producing engineered probiotics ameliorated murine ulcerative colitis by restoring anti‐inflammatory macrophage via the GPR43/HDAC1/IL‐10 axis
Authors: Kang Guangbo , Wang Xiaoli , Gao Mengxue , Wang Lina , Feng Zelin , Meng Shuxian , Wu Jiahao , Zhu Zhixin , Gao Xinran , Cao Xiaocang , Huang He
Published: May 2024

Inflammatory bowel disease (IBD) is a chronic and unspecific inflammatory disorder of the gastrointestinal tract, and current treatment options often fail to maintain long‐term remission. Studies have shown that propionate level is reduced in fecal samples from patients with IBD. Propionate can ameliorate IBD through intestinal epithelial cells and immune regulation, but its effects on the inflammatory microenvironment and macrophage differentiation have not been widely studied. To address this, we constructed an engineered propionate‐producing probiotic (EcNP3) to achieve sustained restoration of propionate levels in the gut and increase its bioavailability. DSS‐induced experimental intestinal inflammation model was used to evaluate the effect of EcNP3 on improving the intestinal mucosal barrier and increasing the proportion of anti‐inflammatory macrophages. It was found that EcNP3 exhibited a restorative effect on the depletion of peritoneal anti‐inflammatory macrophages (F4/80hiCD11bhi) and significantly improved the expression level of IL‐10. Simultaneously, the expression of IL‐1β, IL‐6, and CXCL1 was downregulated while inhibiting apoptosis of tissue‐resident macrophages ex vivo. Further investigation revealed that EcNP3 regulates IL‐10 expression through G protein‐coupled receptor 43 and histone deacetylase. Furthermore, EcNP3 significantly inhibited the protein expression of HDAC1 and promoted the histone acetylation level of cells. Finally, EcNP3 significantly improved DSS‐induced colitis in mice by increasing mucus production and reducing inflammatory infiltration. Our results suggest that the engineered live biotherapeutic product EcNP3 is a safe and potently efficacious treatment for IBD, which defines a novel strategy in IBD therapy through macrophage IL‐10 signaling.
Predictive modeling of on‐time graduation in computing engineering programs: A case study from Northern Chile
Authors: Quelopana Aldo , Keith Brian , Pizarro Ricardo
Published: May 2024

In the ever‐evolving landscape of 21st‐century education, this research seeks to understand the challenges of on‐time graduation for students in two related computing majors. In particular, we focus on the Universidad Católica del Norte computing engineering programs in Chile, specifically the “Computing and Informatics Civil Engineering” (ICCI) and “Computing and Informatics Execution Engineering” (IECI) programs. We developed a machine‐learning‐based model using random forests to predict delays in submissions of the final report of graduation projects, the key step in the graduation pipeline of the analyzed students. We had access to a data set comprised of 209 students in the period from 2013 to 2017, out of these students, only 111 completed all their graduation requirements. Thus, we focused on this subset of students for the analysis. Our analyses of results indicate that individual advisors minimally contribute to predicting timely or late submissions, emphasizing the need for a holistic approach. In contrast, the specific major, graduation modality, and time in the program play crucial roles, with GPA emerging as the most influential factor (24.06%). Notably, the “Professional Work” modality exhibits a moderate positive correlation with late submissions, contextualized by students' employment commitments. The study's predictive model offers actionable insights for educators and administrators, identifying at‐risk students and advocating for personalized support strategies. This research contributes to the ongoing dialogue on enhancing educational outcomes by integrating data‐driven approaches tailored to diverse student profiles.
Prediction of prognosis using artificial intelligence‐based histopathological image analysis in patients with soft tissue sarcomas
Authors: Hagi Tomohito , Nakamura Tomoki , Yuasa Hiroto , Uchida Katsunori , Asanuma Kunihiro , Sudo Akihiro , Wakabayahsi Tetsushi , Morita Kento
Published: May 2024

Background

Prompt histopathological diagnosis with accuracy is required for soft tissue sarcomas (STSs) which are still challenging. In addition, the advances in artificial intelligence (AI) along with the development of pathology slides digitization may empower the demand for the prediction of behavior of STSs. In this article, we explored the application of deep learning for prediction of prognosis from histopathological images in patients with STS.

Methods

Our retrospective study included a total of 35 histopathological slides from patients with STS. We trained Inception v3 which is proposed method of convolutional neural network based survivability estimation. F1 score which identify the accuracy and area under the receiver operating characteristic curve (AUC) served as main outcome measures from a 4‐fold validation.

Results

The cohort included 35 patients with a mean age of 64 years, and the mean follow‐up period was 34 months (2–66 months). Our deep learning method achieved AUC of 0.974 and an accuracy of 91.9% in predicting overall survival. Concerning with the prediction of metastasis‐free survival, the accuracy was 84.2% with the AUC of 0.852.

Conclusion

AI might be used to help pathologists with accurate prognosis prediction. This study could substantially improve the clinical management of patients with STS.
Causal effects of hypertensive disorders of pregnancy on future gynecologic tumors: A two‐sample Mendelian randomization study
Authors: Zhou Le , Liu Xinghui , He Guolin , Sun Chuntang
Published: May 2024

Background

Numerous observational studies have investigated the potential link between hypertensive disorders of pregnancy (HDPs) and the subsequent risks of gynecologic tumors, yet the findings have been inconsistent. In this study, we utilized Mendelian randomization (MR) approach to assess the influence of HDPs on the future risks of ovarian, cervical, endometrial, and breast cancer and uterine fibroids, controlling for confounding factors.

Methods

The genome‐wide association studies (GWAS) summary data relevant to HDPs was obtained from the FinnGen databases (10,736 cases and 136,325 controls). Gynecologic tumor outcomes were extracted from the IEU Open GWAS project and UK Biobank (47,690 cases and 1, 092,073 controls). The inverse variance weighted (IVW) approach was selected as the principal method for MR analysis, supplemented by MR‐Egger, weighted median, weighted model, simple model methods, MR pleiotropy residual sum and outlier (MR‐PRESSO) test, and leave‐one‐out method. Multivariate MR (MVMR) analysis was conducted after adjusting systolic blood pressure (SBP), body mass index (BMI) and type 2 diabetes mellitus (T2DM).

Results

Our univariate MR analysis (UVMR) results revealed no significant relationship between HDPs and the risks of ovarian cancer (odds ratio [OR] = 0.924, p = 0.360), cervical cancer (OR = 1.230, p = 0.738), endometrial cancer (OR = 1.006, p = 0.949), uterine fibroids (OR = 1.155, p = 0.158), and breast cancer (OR = 0.792, p = 0.241) by IVW test. Similar results were observed in gestational hypertension and preeclampsia/eclampsia. Additionally, our study detected neither heterogeneity nor pleiotropy. MVMR analysis also provided no evidence of a causal association between HDPs and common gynecologic tumors after adjusting SBP, BMI, and T2DM.

Conclusion

We discovered no causal relationship between HDPs and ovarian, cervical, endometrial, breast cancer, and uterine fibroids in European populations. However, present analysis did not explore the effect of HDPs on the subtypes of gynecologic tumors across varied ethnic populations, which may require additional research.
The role of programmed cell death in osteosarcoma: From pathogenesis to therapy
Authors: Liu Suqing , Liu Chengtao , Wang Yian , Chen Jiewen , He Yujin , Hu Kaibo , Li Ting , Yang Junmei , Peng Jie , Hao Liang
Published: May 2024

Osteosarcoma (OS) is a prevalent bone solid malignancy that primarily affects adolescents, particularly boys aged 14–19. This aggressive form of cancer often leads to deadly lung cancer due to its high migration ability. Experimental evidence suggests that programmed cell death (PCD) plays a crucial role in the development of osteosarcoma. Various forms of PCD, including apoptosis, ferroptosis, autophagy, necroptosis, and pyroptosis, contribute significantly to the progression of osteosarcoma. Additionally, different signaling pathways such as STAT3/c‐Myc signal pathway, JNK signl pathway, PI3k/AKT/mTOR signal pathway, WNT/β‐catenin signal pathway, and RhoA signal pathway can influence the development of osteosarcoma by regulating PCD in osteosarcoma cell. Therefore, targeting PCD and the associated signaling pathways could offer a promising therapeutic approach for treating osteosarcoma.
Epimedium Linn: A Comprehensive Review of Phytochemistry, Pharmacology, Clinical Applications and Quality Control
Authors: Chen Xiao‐Lin , Li Shi‐Xing , Ge Teng , Zhang Dong‐Dong , Wang Hai‐Fang , Wang Wei , Li Yu‐Ze , Song Xiao‐Mei
Published: May 2024

Epimedium genus is a traditional Chinese medicine, which has functions of tonifying kidney and yang, strengthening tendons and bones, dispelling wind and emoving dampness. It is mainly used for the treatment of impotence and spermatorrhea, osteoporosis, Parkinson's, Alzheimer's, and cardiovascular diseases. The aim of this review is to provide a systematic summary of the phytochemistry, pharmacology, and clinical applications of the Epimedium Linn. In this paper, the relevant literature on Epimedium Linn. was collected from 1987 to the present day, and more than 274 chemical constituents, including flavonoids, phenylpropanoids, lignans, phenanthrenes, and others, were isolated from this genus. Modern pharmacological studies have shown that Epimedium Linn. has osteoprotective, neuroprotective, cardiovascular protective, and immune enhancing pharmacological effects. In addition, Epimedium Linn. has been commonly used to treat osteoporosis, erectile dysfunction, hypertension and cardiovascular disease. In this paper, the distribution of resources, chemical compositions, pharmacological effects, clinical applications and quality control of Epimedium Linn. are progressed to provide a reference for further research and development of the resources of this genus.
Lewis Acid‐Base Interactions as a Racemization Strategy for the Atroposelective Synthesis of (Hetero)biaryls via Dynamic Kinetic Resolution
Authors: Carmona José A. , Rodríguez‐Franco Carlos , Fernández Rosario , Lassaletta José M. , Hornillos Valentín
Published: May 2024

Due to their molecular topology, atropisomers serve as highly valuable chiral frameworks for diverse applications across academic research and industry. Despite the availability of numerous established catalytic methods for their synthesis, there is still a high demand for the development of novel and resourceful strategies. In this concept article, we will detail our studies on the use of transient Lewis acid‐base interactions (LABI) as a dynamization strategy for the synthesis of (hetero)biaryl atropisomers by Dynamic Kinetic Resolution (DKR). The formation of cyclic transition states, resulting from the interaction between an acidic functionality and a basic counterpart, plays a key role in facilitating racemization by substantially reducing the barrier to atropisomerization. In this scenario, we have employed transformations aimed at neutralizing the acidic nature of the Lewis acid, ultimately leading to the formation of configurationally stable enantioenriched compounds. The design of substrates and the employment of stereoselective strategies based on transition metal and biocatalysis for their resolution is detailed. Specific emphasis on the preparation of axially chiral motifs commonly found in catalysis or medicinal chemistry will also be given.
Pilot Scale Pyrolysis and Simulation of Plastic Waste into a Value‐Added Product: An Integrated Approach
Authors: Osman Matin Darwisy , Selimi Nurizzati Erina , Juffri Abdul Bari , Mubarak Nabisab Mujawar , Karri Rama Rao
Published: May 2024

Plastic waste is utilized aggressively for food, product packaging, cosmetics, toys, clothes, and even furniture. As a result, discarded plastic as a waste has grown uncontrollably worldwide, most of it ending up as landfill. With increasing concern, researchers have made efforts to convert this plastic waste into a more useful product. Along these lines, this study focuses on producing 10 tons of diesel per day through fast pyrolysis at 450 °C in the fluidized bed reactor for a feed rate of 3000 kg of plastic waste per hour. The production was simulated in Aspen HYSYS V11 to ensure the desired yield. Further, a detailed economic analysis is carried out to estimate the return on investment and total cost per year, as well as the payback period and the profit for different scenarios.
‘Passivated Precursor’ Approach to All‐Alkynyl‐Protected Gold Nanoclusters and Total Structure Determination of Au130
Authors: Lei Zhen , Zhao Pei , Guan Zong‐Jie , Nan Zi‐Ang , Ehara Masahiro , Wang Quan‐Ming
Published: May 2024

A ‘passivated precursor’ approach is developed for the efficient synthesis and isolation of all‐alkynyl‐protected gold nanoclusters. Direct reduction of dpa‐passivated precursor Au‐dpa (Hdpa=2,2’‐dipyridylamine) in one‐pot under ambient conditions gives a series of clusters including Au22(C≡CR)18 (R=−C6H4−2−F), Au36(C≡CR)24, Au44(C≡CR)28, Au130(C≡CR)50, and Au144(C≡CR)60. These clusters can be well separated via column chromatography. The overall isolation yield of this series of clusters is 40 % (based on gold), which is much improved in comparison with previous approaches. It is notable that the molecular structure of the giant cluster Au130(C≡CR)50 is revealed, which presents important information for understanding the structure of the mysterious Au130 nanoclusters. Theoretical calculations indicated Au130(C≡CR)50 has a smaller HOMO‐LUMO gap than Au130(S−C6H4−4−CH3)50. This facile and reliable synthetic approach will greatly accelerate further studies on all‐alkynyl‐protected gold nanoclusters.
A Sodium Bis(fluorosulfonyl)imide (NaFSI)‐based Multifunctional Electrolyte Stabilizes the Performance of NaNi1/3Fe1/3Mn1/3O2/hard Carbon Sodium‐ion Batteries
Authors: Fan Weizhen , Wang Wenlian , Xie Qixing , He Xin , Li Haijia , Zhao Jingwei , Nan Junmin
Published: May 2024

A sodium bis(fluorosulfonyl)imide (NaFSI)‐based multifunctional electrolyte is developed by partially replacing NaPF6 salt in the electrolyte to improve the wide temperature range working capability of NaNi1/3Fe1/3Mn1/3O2/hard carbon (NNFM111/HC) sodium‐ion batteries (SIBs). The capacity retention of the SIBs with NaFSI‐NaPF6 dual salt electrolyte increases from 47.2 % to 75.5 % after 250 cycles at 25 °C, and from 51.0 % to 82.3 % after 80 cycles at 45 °C, and the 1 C discharge capacity retention at the low temperature of −20 °C also increases 26.8 %. In the single salt system, NaPF6 effectively passivate the aluminum foil and NaFSI passivate the electrode/electrolyte interface. The synergistic effect of NaPF6 and NaFSI greatly improves the battery performance in a wide temperature range. This NaFSI‐based dual salt electrolyte also effectively overcomes the flaws when the SIBs using NaFSI or NaPF6 independently, and makes it more suitable for SIBs, indicating promising prospects in the commercial application of NNFM111/HC SIBs.