bluuebunny/crossref_metadata_2025_split huggingface dataset:
Differential gene expression analysis after DAPK1 knockout in hepatocellular carcinoma cells
Authors: Li Yuanqi , Huang Hui , Yu Huajun , Mo Ting , Wei Ting , Li Guodan , Jia Yufang , Huang Xiaoqin , Tu Mingjin , Yan Xiuwen , Zhang Haitao 
Published: August 2022

Background
The mechanism through which death-associated protein kinase 1 (DAPK1) causes hepatocellular carcinoma (HCC) progression remains unclear. In this study, we aimed to identify key proteins that were altered after DAPK1 knockout.

Methods
Stable DAPK1 knockout HCC cell lines were established, then the differentially expressed genes (DEGs) of HCC were screened using the NetworkAnalyst database and enriched using the Metascape software. Protein-protein interaction networks (PPIs) were analyzed and visualized using the STRING database expansion.

Results
In total, 732 differentially expressed genes were identified, including 415 upregulated genes and 317 downregulated genes. Through Cytoscape software scoring, 10 pivotal genes were found to be closely related to changes in DAPK1 expression; Kininogen-1 (KNG1), Complement C3 (C3), Metalloproteinase inhibitor 1 (TIMP1), and Alpha-2-HS-glycoprotein (AHSG) were the most strongly associated with DAPK1 expression changes. Moreover, western blot analysis results revealed that changes in the levels of proteins encoded by the four key genes after DAPK1 knockout were consistent with those seen in the database screening.

Conclusions
These results provide a direction for further studies on the DAPK1 gene and on the mechanism through which DAPK1 leads to hepatocellular carcinoma development.
Enhanced Performance of Ternary CuGaSe2 Thin‐Film Photovoltaic Solar Cells and Photoelectrochemical Water Splitting Hydrogen Evolution with Modified p–n Heterointerfaces
Authors: Ishizuka Shogo , Okamoto Riku , Ikeda Shigeru 
Published: August 2022

AbstractRenewable energy sources, in particular, photovoltaic solar cells and hydrogen fuel, are expected to be the pillars of a sustainable society. Chalcopyrite CuGaSe2 (CGSe) has potential for using in such applications. This article presents efficient solar cells suitable as top cells for tandem devices and highly active photocathodes for solar hydrogen evolution using CGSe photoabsorber layers with modified p–n heterointerfaces. Rb‐doping during the last stage of CGSe film growth effectively improves the photovoltaic performance, and solar cell efficiency of >10% with a high fill factor (FF) of 74.6% is obtained. The half‐cell solar‐to‐hydrogen conversion efficiency reaches 8% with the use of a photocathode composed of a CGSe film grown in an identical growth batch. Interface modification with i) a Cu‐deficient layer, ii) alkali‐metal doping, and iii) an n‐type buffer layer formed on the CGSe film surface is found to a be key to control the energy conversion device parameters, such as the FF and open circuit voltage of solar cells and the onset potential of photoelectrochemical cells, due to the suppression of interface recombination.
Hydrodynamics and mass transfer enhancement of gas–liquid flow in micropacked bed reactors: Effect of contact angle
Authors: Wang Hongbin , Zhou Tao , Han Shaopeng , Duan Lian , Sang Le , Zhao Zhiping 
Published: August 2022

AbstractPressure drop, residence time distribution, dispersive behavior, liquid holdup, and mass transfer performance of gas–liquid flow in micropacked bed reactors (μPBRs) with different contact angles (CA) of particles are studied. The value of pressure drop for three types of beads can be obtained: copper beads (CA = 88.1°) > stainless steel beads (CA = 70.2°) > glass beads (CA = 47.1°). The liquid axial dispersion coefficient is 1.58 × 10−6 to 1.07 × 10−5 m2/s for glass beads and copper beads, which is smaller than those of trickle bed reactors. The liquid holdup of 400 μm copper beads is larger than that of 400 μm glass beads. The ratio of effective interfacial area enhancement is evaluated up to 55% for big contact angle beads compared with the hydrophilic glass beads. In addition, correlations of pressure drop, liquid holdup, and effective interfacial area in μPBRs with different wettability beads are developed and predicted values are in agreement with the experimental data.
Oxalate Oxidase for In Situ H2O2‐Generation in Unspecific Peroxygenase‐Catalysed Drug Oxyfunctionalisations**
Authors: Romero Elvira , Johansson Magnus J. , Cartwright Jared , Grogan Gideon , Hayes Martin A. 
Published: August 2022

AbstractH2O2‐driven enzymes are of great interest for industrial biotransformations. Herein, we show for the first time that oxalate oxidase (OXO) is an efficient in situ source of H2O2 for one of these biocatalysts, which is known as unspecific peroxygenase (UPO). OXO is reasonably robust, produces only CO2 as a by‐product and uses oxalate as a cheap sacrificial electron donor. UPO has significant potential as an industrial catalyst for selective C−H oxyfunctionalisations, as we confirm herein by testing a diverse drug panel using miniaturised high‐throughput assays and mass spectrometry. 33 out of 64 drugs were converted in 5 μL‐scale reactions by the UPO with OXO (conversion >70 % for 11 drugs). Furthermore, oxidation of the drug tolmetin was achieved on a 50 mg scale (TONUPO 25 664) with 84 % yield, which was further improved via enzyme immobilization. This one‐pot approach ensures adequate H2O2 levels, enabling rapid access to industrially relevant molecules that are difficult to obtain by other routes.
Diastereo‐ and Enantioselective Construction of Vicinal All‐Carbon Quaternary Stereocenters via Iridium/Europium Bimetallic Catalysis
Authors: Wang Wei , Zhang Fangqing , Liu Yangbin , Feng Xiaoming 
Published: August 2022

AbstractThe diastereo‐ and enantioselective construction of vicinal all‐carbon quaternary stereocenters is a formidable task. We here report a synergistic bimetallic catalysis via a chiralN,N′‐dioxide‐europium (Eu) complex and a phosphoramidite‐iridium (Ir) catalyst for the asymmetric allylation of oxindole derivatives by using challenging trisubstituted allylic esters. The allylated products bearing vicinal all‐carbon quaternary stereocenters were obtained with good diastereoselectivities (up to 20 : 1 dr) and excellent enantioselectivities (up to 99 % ee). Control experiments showed that the complementary diastereomers of the products were not accessible by the change of the stereochemistry of the chiralN,N′‐dioxide ligand.
Cobalt/Salox‐Catalyzed Enantioselective Dehydrogenative C−H Alkoxylation and Amination
Authors: Chen Jia‐Hao , Teng Ming‐Ya , Huang Fan‐Rui , Song Hong , Wang Zhen‐Kai , Zhuang He‐Lin , Wu Yong‐Jie , Wu Xu , Yao Qi‐Jun , Shi Bing‐Feng 
Published: August 2022

AbstractThe past decade has witnessed a rapid progress in asymmetric C−H activation. However, the enantioselective C−H alkoxylation and amination with alcohols and free amines remains elusive. Herein, we disclose the first enantioselective dehydrogenative C−H alkoxylation and amination enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The use of cheap and readily available cobalt(II) salts as catalysts and Saloxs as chiral ligands provides an efficient method to access P‐stereogenic compounds in excellent enantioselectivities (up to >99 % ee). The practicality of this protocol is demonstrated by gram‐scale preparation and further derivatizations of the resulting P‐stereogenic phosphinamides, which offering a flexible asymmetric alternative to access P‐stereogenic mono‐ and diphosphine chiral ligands. Preliminary mechanistic studies on the enantioselective C−H alkoxylation reaction suggest that a cobalt(III/IV/II) catalytic cycle might be involved.
Green and Scalable Fabrication of High‐Performance Biocatalysts Using Covalent Organic Frameworks as Enzyme Carriers
Authors: Zheng Yunlong , Zhang Sainan , Guo Jinbiao , Shi Ruixuan , Yu Jiangyue , Li Kaipeng , Li Ning , Zhang Zhenjie , Chen Yao 
Published: August 2022

AbstractEnzyme immobilization is essential to the commercial viability of various critical large‐scale biocatalytic processes. However, challenges remain for the immobilization systems, such as difficulties in loading large enzymes, enzyme leaching, and limitations for large‐scale fabrication. Herein, we describe a green and scalable strategy to prepare high‐performance biocatalysts through in situ assembly of enzymes with covalent organic frameworks (COFs) under ambient conditions (aqueous solution and room temperature). The obtained biocatalysts have exceptional reusability and stability and serve as efficient biocatalysts for important industrial reactions that cannot be efficiently catalyzed by free enzymes or traditional enzyme immobilization systems. Notably, this versatile enzyme immobilization platform is applicable to various COFs and enzymes. The reactions in an aqueous solution occurred within a short timeframe (ca. 10–30 min) and could be scaled up readily (ca. 2.3 g per reaction).
Microfluidic‐assisted preparation of nano and microscale chitosan based 3D composite materials: Comparison with conventional methods
Authors: Kimna Ceren , Deger Sibel , Tamburaci Sedef , Tihminlioglu Funda 
Published: August 2022

AbstractAlthough nanofillers contribute to improved physical characteristics and biological functionalities of polymer‐based biomaterials, their dispersion in polymer matrices is still a challenging issue in terms of obtaining consistency for the inherent properties. To tackle this problem, homogenization techniques are applied to disperse the nanofillers in such polymers, however, these methods can cause undesired changes especially in the rheological properties and the physical structure of the biopolymer matrices. Recently, as a novel homogenization technique, microfluidization has been used to homogenize polymer nanocomposites to minimize these limitations. In this study, two different nanocomposite structures as chitosan/montmorillonite (CS/MMT) and chitosan/polyhedral oligomeric silsesquioxane nanocages (CS/POSS) were homogenized with microfluidization and investigated in terms of physical alterations. Furthermore, the effect of microfluidizer technique on material characteristics was compared with conventional homogenization techniques, i.e., ultrasonic bath and sonication in terms of solution, nano – (e.g., hydrodynamic size, drug encapsulation) and macroscopic material characteristics (e.g., porosity, mechanical properties, swelling and thermal degradation). It was found that the microfluidizer homogenization improves the physical characteristics in both nano and macroscale materials: Nanospheres obtained from CS/MMT composites showed enhanced stability, uniform size distribution (<100 nm, PDI: <0.2), and good encapsulation efficiency (>50%) whereas 3D porous CS/POSS scaffolds showed improved structural uniformity (i.e., homogeneous and interconnected microstructure) and enhanced thermal and mechanical properties. The obtained results indicate that the microfluidizer homogenization ensures a successful nanofiller dispersion in polymer matrices, thereby improving the biomaterial characteristics impressively compared to the sonication methods.
Endostructural and periosteal growth of the human humerus
Authors: O'Mahoney Thomas George , Lowe Tristan , Chamberlain Andrew Timothy , Sellers William Irvin 
Published: August 2022

AbstractThe growth and development of long bones are of considerable interests in the fields of comparative anatomy and palaeoanthropology, as evolutionary changes and adaptations to specific physical activity patterns are expected to be revealed during bone ontogeny. Traditionally, the cross‐sectional geometry of long bones has been examined at discrete locations usually placed at set intervals or fixed percentage distances along the midline axis of the bone shaft. More recently, the technique of morphometric mapping has enabled the continuous analysis of shape variation along the shaft. Here we extend this technique to the full sequence of late fetal and postnatal development of the humeral shaft in a modern human population sample, with the aim of establishing the shape changes during growth and their relationship with the development of the arm musculature and activity patterns. A sample of modern human humeri from individuals of age ranging from 24 weeks in utero to 18 years was imaged using microtomography at multiple resolutions and custom Matlab scripts. Standard biomechanical properties, cortical thickness, surface curvature, and pseudo‐landmarks were extracted along radial vectors spaced at intervals of 1° at each 0.5% longitudinal increment measured along the shaft axis. Heat maps were also generated for cortical thickness and surface curvature. The results demonstrate that a whole bone approach to analysis of cross‐sectional geometry is more desirable where possible, as there is a continuous pattern of variation along the shaft. It is also possible to discriminate very young individuals and adolescents from other groups by relative cortical thickness, and also by periosteal surface curvature.
Metabolic profiling of soyasaponin Bb in rat plasma, urine, bile, and feces after intragastric administration
Authors: Yu Xinwei , Wu Yuchen , Wang Yuzhen , Cheng Yu , Xiang Zheng 
Published: August 2022

AbstractSoyasaponin Bb is one of the bioactive oleanolic acid–type triterpenoid saponins mainly isolated from soybean. It possesses significant antithrombosis, hypolipidemic, anticancer, and antioxidant activities. However, the metabolic profiles of soyasaponin Bb are still unknown. The present study investigated the metabolites of soyasaponin Bb in plasma, bile, urine, and feces samples after intragastric administration using ultra‐performance liquid chromatography coupled with quadrupole‐time‐of‐flight‐mass spectrometry, and its possible metabolic pathways were subsequently proposed. Using the metabolite profiling strategy, 11 metabolites were first identified from urine, plasma, bile, and feces of rats after intragastric administration of soyasaponin Bb. Hydroxylation and hydrolysis were the major metabolic pathways of soyasaponin Bb in rat. The results expand our knowledge of the metabolism of soyasaponin Bb, which could provide valuable information for better comprehension of future pharmacological research.
Quantification of SHR0302 in human plasma by UPLC–MS/MS and application to a pharmacokinetic study
Authors: Ding Li‐kun , Chen Yan , Liu Mei‐you , Gao Xiao‐hua , Ren Dan‐jun , Diao Qing‐bo , Yang Lin , Wen Ai‐dong , Wang Jing‐wen 
Published: August 2022

AbstractSHR0302, as a novel Janus kinase (JAK) inhibitor 1, is used for treatment of rheumatoid arthritis (RA) in humans. A novel and sensitive ultra‐high performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) has been developed and validated for determining the concentration of SHR0302 in human plasma. A precipitation deproteinization method was used for plasma pretreatment with methanol. Detection was carried out on an Agilent 1,260 UPLC coupled with a Triple Quad 4000 mass spectrometer operated in positive multiple reaction monitoring mode, and the analytes were separated on a Synergi Polar‐RP C18 (50 × 2.0 mm, 4 μm, Phenomenex) analytical column with gradient elution of 0.1% formic acid, and 2 mmol/l ammonium acetate in water and 0.1% formic acid and 2 mmol/l ammonium acetate in methanol, The selected ion transitions were m/z 415.2 → 258.2 and m/z 398.2 → 258.2 for SHR0302 and SHR143181 (internal standard), respectively. A full validation, including selectivity, linearity, carryover, precision, accuracy, recovery, matrix effect, dilution integrity and stability, was carried out in human plasma. It was successfully applied to a pharmacokinetic study in Chinese healthy subjects after oral administration of SHR0302 tablet.
Microkinetic Modeling of the Transient CO2 Methanation with DFT‐Based Uncertainties in a Berty Reactor
Authors: Kreitz Bjarne , Wehinger Gregor D. , Goldsmith C. Franklin , Turek Thomas 
Published: August 2022

AbstractThe transient operation of methanation reactors can become desirable when coupled with fluctuating renewable energies in Power‐to‐Gas scenarios, which requires suitable kinetic approaches that can describe the transient catalytic phenomena. A combined experimental and theoretical investigation of the transient CO2 methanation is conducted using concentration forcing to derive a suitable microkinetic model. Methanation experiments are performed with a Ni/SiO2 catalyst in a Berty‐type reactor at industrially relevant conditions. The microkinetics are based on previous work and were automatically constructed for the Ni(111) facet using the Reaction Mechanism Generator. A feasible set of energetic parameters of the microkinetic models was identified in a theory‐constrained optimization procedure within the DFT uncertainty space that can accurately reproduce the experimental results on a first‐principles basis. The microkinetic model unravels that the formation of H2O* and CH3* control the activity and selectivity of Ni(111) under the investigated conditions.
Electronic Metal‐Support Interaction Strengthened Pt/CoAl‐LDHs Catalyst for Selective Cinnamaldehyde Hydrogenation
Authors: Gao Zhexi , Cai Luoyu , Miao Chenglin , Hui Tianli , Wang Qian , Li Dianqing , Feng Junting 
Published: August 2022

AbstractCinnamaldehyde (CAL) is a typical sustainable biomass molecule which is classified as α, β‐unsaturated aldehydes. Selective hydrogenation of CAL to produce high‐value and fine chemical cinnamylalcohol (COL) is an attractive catalytic transformation process. However, the hydrogenation of C=O bond in CAL is more unfavorable than C=C bond in thermodynamics and kinetics, leading to great challenge on achieving high yield of unsaturated alcohol. In this work, a Pt/CoAl‐LDHs catalyst was prepared for hydrogenation of CAL to COL, showing outstanding intrinsic activity (TOF as high as 4.93 s−1) and finally achieving 93.6 % selectivity at 95.4 % conversion. In contrast, the yields of COL over Pt/Co(OH)2 and Pt/Al(OH)3 were only 73 % and 34 % respectively. Characterizations including Raman, O‐XAFS, XPS revealed that the Co2+−O2−−Al3+ structure in CoAl‐LDHs contributed to strengthened metal‐support interactions, and resulted in electron‐rich and geometric decoration Ptδ− sites. The electron‐rich Ptδ− provided preferable H2 activation capability, and also exposed abundant unsaturated sites which optimized the adsorption mode of cinnamaldehyde favorable for C=O hydrogenation. However, in Pt/Co(OH)2 and Pt/Al(OH)3 catalysts, the Pt0 without electron‐rich and unsaturated property cannot improve the H2 activation capability as well as electronic repellency to C=C bond. In addition, a possible catalytic mechanism was proposed to illustrate the role of Ptδ−−Co2+−O2−−Al3+ interfacial structure on enhancing activity and selectivity.
Revealing the Heterogeneity of Large‐Area MoS2Layers in the Electrocatalytic Hydrogen Evolution Reaction
Authors: Schumacher Simon , Madauß Lukas , Liebsch Yossarian , Tetteh Emmanuel Batsa , Varhade Swapnil , Schuhmann Wolfgang , Schleberger Marika , Andronescu Corina 
Published: August 2022

AbstractThe electrocatalytic activity concerning the hydrogen evolution reaction (HER) of micrometer‐sized MoS2layers transferred on a glassy carbon surface was evaluated by scanning electrochemical cell microscopy (SECCM) in a high‐throughput approach. Multiple areas on single or multiple MoS2layers were assessed using a hopping mode nanocapillary positioning with a hopping distance of 500 nm and a nanopipette size of around 55 nm. The locally recorded linear sweep voltammograms revealed a high lateral heterogeneity over the MoS2sheet regarding their HER activity, with currents between −40 and −60 pA recorded at −0.89 V vs. reversible hygrogen electrode over about 4400 different measured areas on the MoS2sheet. Stacked MoS2layers did not show different electrocatalytic activity than the single MoS2sheet, suggesting that the interlayer resistance influences the electrocatalytic activity less than the resistances induced by possible polymer residues or water layers formed between the transferred MoS2sheet and the glassy carbon electrode.
Fabrication of Highly Luminescent and Thermally Stable Phosphors through In‐Situ Formation of BaSO4 on Sulfur Nanodots
Authors: Guo Jiaqi , Feng Anrui , Shi Yu‐e , Wang Zhenguang 
Published: August 2022

AbstractProducing high performance phosphors using abundant and non‐toxic precursors yet straightforward methods are promising but still a challenging task. Herein, highly luminescent and thermally stable phosphors were fabricated through an in situ precipitation synthesis strategy. Sulfur nanodots (S‐dots) act as the precursors for precipitation reactions and also provide the luminescent centers. Structural and optical characterization investigations suggest that S‐dots are incorporated in the matrix of BaSO4, and BaSO4 provides passivation effect for the surface ligands or traps of S‐dots. This results in the promotion of photoluminescence quantum yield from 23 % to 58 %, and the BaSO4 matrix also leads to the obvious promotion of thermal stability. These merits endow the construction of phosphor‐based light‐emitting diodes by utilizing the S‐dots@BaSO4 hybrid phosphors as a color conversion layer. These research results are significant for developing sulfur‐based luminescent materials, and also provide a solid and universal theory to produce high quality phosphors.
Asymmetric Alkylation of Cyclic Ketones with Dehydroalanine via H‐Bond‐Directing Enamine Catalysis: Straightforward Access to Enantiopure Unnatural α‐Amino Acids
Authors: Retini Michele , Bartolucci Silvia , Bartoccini Francesca , Piersanti Giovanni 
Published: August 2022

AbstractThe growing importance of structurally diverse and functionalized enantiomerically pure unnatural amino acids in the design of drugs, including peptides, has stimulated the development of new synthetic methods. This study reports the challenging direct asymmetric alkylation of cyclic ketones with dehydroalanine derivatives via a conjugate addition reaction for the synthesis of enantiopure ketone‐based α‐unnatural amino acids. The key to success was the design of a bifunctional primary amine‐thiourea catalyst that combines H‐bond‐directing activation and enamine catalysis. The simultaneous dual activation of the two relatively unreactive partners, confirmed by mass spectrometry studies, results in high reactivity while securing high levels of stereocontrol. A broad substrate scope is accompanied by versatile downstream chemical modifications. The mild reaction conditions and consistently excellent enantioselectivities (>95 % ee in most cases) render this protocol highly practical for the rapid construction of valuable noncanonical enantiopure α‐amino‐acid building blocks.