bluuebunny/crossref_metadata_2025 huggingface dataset:
Cationic and Anionic Redox of Battery Cathodes Investigated by Advanced Synchrotron‐Based Mapping of Resonant Inelastic X‐ray Scattering
Authors: Cheng Chen , Zhuo Zengqing , Chen Shuyuan , Zhou Xi , Yuan Cheng , Zeng Pan , Guo Jinghua , Zhang Liang
Published: April 2024

Redox reaction builds the foundation stone for the energy density of rechargeable battery cathodes. Probing and understanding the redox reaction behavior is crucial, but also extremely formidable, which requires individual and reliable detection of cationic and anionic redox states. Fortunately, the recently developed ultra‐high‐efficiency mapping of resonant inelastic X‐ray scattering (mRIXS) has emerged as a powerful tool to probe the battery chemistry states. Here, the latest advances of employing advanced mRIXS is summarized to investigate the cationic and anionic redox mechanism of battery cathodes during electrochemical operation. Owing to the new dimension of information along the emission energy and high sensitivity to valence 3d states, 3d transition‐metal L‐edge (TM‐L) mRIXS can eliminate the lineshape distortion in conventional 3d TM‐L fluorescence X‐ray absorption spectra and investigate the cationic redox quantitatively. Moreover, O‐K mRIXS could fingerprint the intrinsic oxidized lattice oxygen states and quantify the oxygen redox (OR) reversibility, thus demystifying the controversy in traditional wisdom. In addition, different modification strategies coupled with underlying mechanisms for regulating the activity and reversibility of OR utilizing mRIXS are also summarized. This review provides valuable guidance for further exploration of underlying reaction mechanisms of battery cathodes by mRIXS, along with both technological and scientific improvements.
Plant Tattoo Sensor Array for Leaf Relative Water Content, Surface Temperature, and Bioelectric Potential Monitoring
Authors: Yin Shihao , Dong Liang
Published: April 2024

This study presents a wearable plant tattoo sensor array designed for continuous monitoring of leaf temperature, relative water content, and biopotential. Current plant wearable sensor technologies often require relatively bulky substrates for sensor support and adhesives for leaf attachment, which potentially can hinder plant growth and affect long‐term measurements. The multifunctional tattoo sensor array overcomes these issues by adhering directly to the leaf surface without the need for additional supporting structures or glues. This array includes a biopotential electrode, a resistive temperature sensor, and an impedimetric water content sensor, all constructed using laminated gold‐on‐polymer thin‐film patterns. Due to their mechanical flexibility, stretchability, and conformability, the sensors can seamlessly attach to leaves via van der Waals force. Performances of these sensors are evaluated to explore plant responses under diverse growth environments. This sensor array is capable of both short‐term and long‐term monitoring, offering continuous data and detailed insights into plant physiological responses to various stress conditions.
Pd8(PDip)6: Cubic, Unsaturated, Zerovalent
Authors: Breitwieser Kevin , Bevilacqua Matteo , Mullassery Sneha , Dankert Fabian , Morgenstern Bernd , Grandthyll Samuel , Müller Frank , Biffis Andrea , Hering‐Junghans Christian , Munz Dominik
Published: April 2024

Atomically precise nanoclusters hold promise for supramolecular assembly and (opto)electronic‐ as well as magnetic materials. Herein, this work reports that treating palladium(0) precursors with a triphosphirane affords strongly colored Pd8(PDip)6 that is fully characterized by mass spectrometry, heteronuclear and Cross‐Polarization Magic‐Angle Spinning (CP‐MAS) NMR‐, infrared (IR), UV–vis, and X‐ray photoelectron (XP) spectroscopies, single‐crystal X‐Ray diffraction (sc‐XRD), mass spectrometry, and cyclovoltammetry (CV). This coordinatively unsaturated 104‐electron Pd(0) cluster features a cubic Pd8‐core, µ4‐capping phosphinidene ligands, and is air‐stable. Quantum chemical calculations provide insight to the cluster's electronic structure and suggest 5s/4d orbital mixing as well as minor Pd─P covalency. Trapping experiments reveal that cluster growth proceeds via insertion of Pd(0) into the triphosphirane. The unsaturated cluster senses ethylene and binds isocyanides, which triggers the rearrangement to a tetrahedral structure with a reduced frontier orbital energy gap. These experiments demonstrate facile cluster manipulation and highlight non‐destructive cluster rearrangement as is required for supramolecular assembly.
Effect of cotton population density on lint yield and fiber quality
Authors: Kimura Emi , Adams Curtis , DeLaune Paul , Ramirez Jonathan , Thapa Santanu
Published: April 2024

Commercial cultivars with advanced technology have reduced pest pressures, while greater seed costs have increased total production cost. Limited information is available on the optimal final population density (PD) for the commercially available cotton (Gossypium hirsutum L.) cultivars with advanced technologies in water‐scarce environments. Therefore, our objectives were to examine the effects of PD on cotton growth and development, lint yield, fiber quality, and net return. A 2‐year study was conducted to test four PDs (low, medium, high, and very high) in deficit‐irrigated and dryland conditions at Chillicothe, TX. Final PD at 12 days after planting were 54,078, 109,563, 124,037, and 151,377 plant ha−1 in irrigated and 67,346, 115,335, 116,397, and 145,432 plant ha−1 in dryland trials. Maturity was delayed in the low PD early in the season; however, the differences on maturity ceased toward the end of the season. No statistical differences were observed on lint yield and fiber quality among treatments in irrigated and dryland trials. Average lint yields were 1199 kg ha−1 in irrigated and 796 kg ha−1 in dryland trial. Net returns were similar among all PD in the irrigated trial, while low PD had significantly higher net‐return than very high PD in the dryland trial. The higher net return at the low PD was due to the lower seed cost associated with a low seeding rate. In the water‐scarce environment, final plant density of 54,078 plant ha−1 in deficit irrigation and 67,346 plant ha−1 in dryland produced optimal yield and net return as compared to higher PD examined.
Relationship between postoperative biliary complications and biliary anatomical aspects in performing right anterior‐ or central bisectionectomy: Single‐center retrospective observational study
Authors: Ueno Masaki , Hayami Shinya , Miyamoto Atsushi , Okada Ken‐ichi , Kitahata Yuji , Shimizu Atsushi , Motobayashi Hideki , Matsumoto Kyohei , Kawai Manabu
Published: April 2024

Aim

Central liver resections are considered to be high‐risk procedures due to postoperative biliary complications. However, anatomical aspect‐related causes are underreported. Focusing upon right anterior sectionectomy (H58) and central bisectionectomy (H458), we assessed risk factors for postoperative biliary complications.

Methods

We retrospectively reviewed patients who underwent H58 or H458 in our hospital between April 2008 and June 2023 (n = 58). We conducted univariate and multivariate analysis of risk factors of postoperative biliary complications among perioperative factors and anatomical factors including the branching type of the right posterior hepatic duct (RPHD) and the length of the right hepatic duct (RHD).

Results

Twenty‐six patients (44.8%) had postoperative biliary complications. Potent risk factors in univariate analysis were the tumor proximity to the right anterior Glissonean branch and longer RHD (both P < 0.01). In multivariate analysis, longer RHD was the only independent risk factor and its hazard (95% confidence interval [CI] was 1.19 (1.05–1.35). Receiver operating characteristics curve (ROC) analysis and the area under the ROC showed that 10 mm was the optimal cutoff value with high discriminatory power (0.72). Considering intraoperative procedures of the right anterior segment Glissonean branch dissection, mass ligation at the second‐order branch had marginal risk, especially in patients with RHD >10 mm; its hazard (95% CI) was 5.83 (0.95–35.7).

Conclusion

Anatomical factors of RPHD and RHD influenced postoperative biliary complications in this cohort. The supraportal with RHD type was most common anatomy but considered to be hazardous if the RHD was >10 mm.
Meta‐Selective Copper‐Catalyzed C−H Arylation of Pyridines and Isoquinolines through Dearomatized Intermediates
Authors: Guo Shu‐Min , Xu Pengwei , Studer Armido
Published: April 2024

C(sp2)−H functionalization offers an efficient strategy for the synthesis of various elaborated N‐containing heteroarenes. Along these lines, oxazino pyridines that can be readily prepared from pyridines, have been introduced as powerful substrates in radical‐ and ionic‐mediated meta‐C−H functionalization. However, the regioselective meta‐C−H arylation of pyridines remains a great challenge. Herein, a copper‐catalyzed meta‐selective C−H arylation of pyridines and isoquinolines through bench‐stable dearomatized intermediates is reported. Electrophilic aryl‐Cu(III) species, generated from readily accessible aryl I(III) reagents, enable the efficient meta‐arylation of a broad range of pyridines and isoquinolines. The method also allows the meta‐selective alkenylation of these heteroarenes using the corresponding alkenyl I(III)‐reagents. Late‐stage arylation of drug‐derived pyridines and larger‐scale experiments demonstrate the potential of this synthetic methodology.
Photo‐Induced Ruthenium‐Catalyzed C−H Arylation Polymerization at Ambient Temperature
Authors: Michiyuki Takuya , Maksso Isaac , Ackermann Lutz
Published: April 2024

Transition metal‐catalyzed C−H arylation polymerization (CHAP) is an attractive tool for constructing π‐conjugated polymers in a sustainable manner. However, the existing methods primarily rely on palladium catalysis, which usually entails harsh reaction conditions and branching/cross‐linking. Here we report the first example of an ambient‐temperature ruthenium‐catalyzed C−H arylation polymerization induced by visible light irradiation. The present polymerization can produce various meta‐ and para‐linked polymers in excellent yields with high molecular weights. The remarkable feature of our mild reaction platform is represented by high chemoselectivity, leading to polymers that are otherwise inaccessible under conventional reaction conditions at high temperatures.
Radical Homopolymerization of Linear α‐Olefins Enabled by 1,4‐Cyano Group Migration
Authors: An Bang , Zhou Litao , Liu Shuai , Zheng Yaxin , Li Changhu , Cui Feichen , Yue Chaowei , Liu Hua , Sui Yang , Ji Chonglei , Yan Jiajun , Li Yifan
Published: April 2024

α‐Olefins are valued and abundant building blocks from fossil resources. They are widely used to provide small‐molecule or polymeric products. Despite numerous advantages of radical polymerization, it has been well‐documented as textbook knowledge that α‐olefins and their functionalized derivatives cannot be radically homopolymerized because of the degradative chain transfer side reactions. Herein, we report our studies on the homopolymerization of thiocyanate functionalized α‐olefins enabled by 1,4‐cyano group migration under radical conditions. By this approach, a library of ABC sequence‐controlled polymers with high molecular weights can be prepared. We can also extend this strategy to the homopolymerization of α‐substituted styrenic and acylate monomers which are known to be challenging to achieve. Overall, the demonstrated functional group migration radical polymerization could provide new possibilities to synthesize polymers with unprecedented main chain sequences and structures. These polymers are promising candidates for novel polymeric materials.
Zinc‐Substituted Hemoglobin–Albumin Cluster as a Porphyrin‐Carrier for Enhanced Photodynamic Therapy
Authors: Yamada Taiga , Katsumi Maho , Ishii Kota , Komatsu Teruyuki
Published: April 2024

Apohemoprotein is focused on the field of theranostics, serving as a porphyrin carrier. Hemoglobin (Hb) consists of α2β2 tetramer with iron(II)‐protoporphyrin IX (heme) bound to each globin. However, heme‐removed Hb (apoHb) causes dissociation at αβ interfaces and aggregation under physiological conditions. We synthesized a stable apoHb derivative comprising intramolecular‐crosslinked apoHb (apoXHb) and human serum albumin (HSA), apoXHb‐HSA3. ApoXHb‐HSA3 engendered no aggregates in the physiological solutions. Moreover, apoXHb‐HSA3 was reconstituted with zinc(II)‐protoporphyrin IX (ZnP), generating ZnXHb‐HSA3, a potent photosensitizer for photodynamic therapy (PDT). The photophysical properties of ZnXHb‐HSA3 were identical to those of zinc‐substituted XHb (ZnXHb). Cellular uptake behavior was evaluated using various cancer cell lines. ZnXHb‐HSA3 released ZnP around the cells, and the free ZnP penetrated cell membranes. In contrast, protein units were not observed within the cells. ZnXHb‐HSA3 showed no cytotoxicity under dark conditions and demonstrated superior PDT activity in comparison to naked ZnXHb. ZnXHb‐HSA3 acts as an innovative porphyrin carrier for enhanced PDT.
Novel enzyme‐resistant pancreatic polypeptide analogs evoke pancreatic beta‐cell rest, enhance islet cell turnover, and inhibit food intake in mice
Authors: Zhu Wuyun , Tanday Neil , Lafferty Ryan A. , Flatt Peter R. , Irwin Nigel
Published: April 2024

Pancreatic polypeptide (PP) is a postprandial hormone secreted from pancreatic islets that activates neuropeptide Y4 receptors (NPY4Rs). PP is known to induce satiety but effects at the level of the endocrine pancreas are less well characterized. In addition, rapid metabolism of PP by dipeptidyl peptidase‐4 (DPP‐4) limits the investigation of the effects of the native peptide. Therefore, in the present study, five novel amino acid substituted and/or fatty acid derivatized PP analogs were synthesized, namely [P3]PP, [K13Pal]PP, [P3,K13Pal]PP, [N‐Pal]PP, and [N‐Pal,P3]PP, and their impact on pancreatic beta‐cell function, as well as appetite regulation and glucose homeostasis investigated. All PP analogs displayed increased resistance to DPP‐4 degradation. In addition, all peptides inhibited alanine‐induced insulin secretion from BRIN‐BD11 beta cells. Native PP and related analogs (10−8 and 10−6 M), and especially [P3]PP and [K13Pal]PP, significantly protected against cytokine‐induced beta‐cell apoptosis and promoted cellular proliferation, with effects dependent on the NPY4R for all peptides barring [N‐Pal,P3]PP. In mice, all peptides, except [N‐Pal]PP and [N‐Pal,P3]PP, evoked a dose‐dependent (25, 75, and 200 nmol/kg) suppression of appetite, with native PP and [P3]PP further augmenting glucagon‐like peptide‐1 (GLP‐1) and cholecystokinin (CCK) induced reductions of food intake. The PP peptides had no obvious detrimental effect on glucose tolerance and they did not noticeably impair the glucose‐regulatory actions of GLP‐1 or CCK. In conclusion, Pro3 amino acid substitution of PP, either alone or together with mid‐chain acylation, creates PP analogs with benefits on beta‐cell rest, islet cell turnover, and energy regulation that may be applicable to the treatment of diabetes and obesity.
Metabolome–microbiome insights into therapeutic impact of 8‐O‐acetylharpagide against breast cancer in a murine model
Authors: Qian Jiahui , Zhao Xinyu , Yuan Siyuan , Su Sijia , Chen Chang , Gao Junfeng , Tang Xu , Men Siye , Wen Binyu
Published: April 2024

Iridoid glycosides extract, which is the main active extract of Ajuga decumbens Thunb, has been proved to have anti‐breast cancer activity in previous studies. However, it is still unknown whether 8‐O‐acetylharpagide, a main active compound in the extract, has anti‐breast cancer activity. In this study, 4 T1 breast cancer mice model was first successfully established. Then the anti‐breast cancer effect of 8‐O‐acetylharpagide was systematically investigated. Feces were collected for metabolomics and 16S rRNA analysis to assess the potential mechanism. The results showed that 8‐O‐acetylharpagide was effective in reducing 4 T1 mouse tumor volume and weight compared with the model group. Metabolome analysis revealed 12 potential metabolite biomarkers in feces, mainly involved in primary bile acid biosynthesis and arachidonic acid metabolism. The 16S rRNA sequencing results demonstrated that 8‐O‐acetylharpagide modulated the abundance of the intestinal flora in 4 T1 mice. Spearman correlation analysis showed that calcitriol and prostaglandin G2 strongly correlated with Akkermansia, Firmicutes and Muribaculum. Overall, the active compound 8‐O‐acetylharpagide could inhibit significantly breast cancer growth in 4 T1 breast cancer model mice. The mechanism of the anti‐breast cancer effect of 8‐O‐acetylharpagide may be related to the regulation of primary bile acid biosynthesis and arachidonic acid metabolism and modulation of the abundance of Akkermansia and Firmicutes.
Sustainability competence in small and medium exporters: Determinant and outcomes
Authors: Chang Hsing‐Hua Stella
Published: April 2024

The pursuit of sustainability has become critical for exporting small and medium enterprises (SMEs), driven by stakeholder pressure and international buyer requirements. This poses challenges to their survival and performance in international markets. Drawing on the capabilities perspective, the present research pioneers the study of this issue by proposing and empirically validating a theoretical framework for the determinant and outcomes of sustainability competence in exporting SMEs. Results from 673 SMEs demonstrate that sustainability orientation drives the configuration of sustainability competence, resulting in enhanced environmental and market performance. Market performance (market legitimacy and brand equity) significantly enhances financial performance, emphasizing the importance of customer satisfaction and investor support. Although no direct causal relationship exists between environmental performance and financial performance, a significant positive correlation is observed. This study thus provides avenues for further research on factors, mechanisms, and contingencies influencing the relationship between environmental performance and financial performance in exporting SMEs.
Two‐pronged reversal of chemotherapy resistance by gold nanorods induced mild photothermal effect
Authors: Shang Qi , Chen Ziyan , Li Jing , Guo Mingmei , Yang Jiapei , Jin Zhu , Shen Yuanyuan , Guo Shengrong , Wang Feihu
Published: April 2024

Chemotherapy treatment outcomes are severely restricted by multidrug resistance (MDR), in which tumors develop a multiple cross‐resistance toward drug involving the pump and nonpump resistance mechanisms, resulting in drug efflux and defending against drug toxicity. Herein, we constructed a pH and near infrared (NIR) light responsive nanomedicine DOX@FG based on gold nanorods (GNRs) that demonstrated the potential to improve chemotherapy outcomes by overcoming MDR. DOX@FG was constructed by conjugating folic acid (FA) and doxorubicin (DOX) derivatives onto GNRs, where the DOX derivatives possessed an acid‐labile hydrazone bond. Stimulated by the acidic media in endocytic organelles, DOX@FG exhibited a responsive dissociation for the controlled release of chemotherapeutic DOX. Surprisingly, we found the mild photothermal effect elicited by GNRs under NIR irradiation simultaneously inhibited the pump and nonpump resistance mechanisms, enhancing the intracellular DOX accumulation and sensitizing the cancer cells to DOX, collectively amplify the chemotherapy efficacy and delay the MCF‐7/ADR breast tumor growth. This intelligent DOX@FG nanomedicine with the potential for two‐pronged reversal of MDR may provide a prospective way to encourage chemotherapy efficacy.
Three‐dimensional reconstruction of King Henri IV's paranasal sinuses and mastoid cells
Authors: Baudouin Robin , Amelot Angélique , Huynh‐Charlier Isabelle , Lisan Quentin , Hans Stéphane , Charlier Philippe
Published: April 2024

Purpose

The preserved head of King Henri IV of France (life 1553–1610, reign 1589–1610) has survived to the present day thanks to high‐quality embalming and favorable conservation conditions. The aim of this study was to examine Henry IV's upper resonant cavities and mastoids using an original and innovative forensic three‐dimensional segmentation method.

Methods

The paranasal sinuses and mastoid cells of King Henri IV of France were studied by cross‐referencing available biographical information with clinical and flexible endoscopic examination and computed tomography (CT‐scan) imaging. The paranasal sinuses and mastoid cells were delineated and their volumes were assessed using ITK‐SNAP 4.0 software (open‐source). Graphical representations were created using Fusion 360® (Autodesk Inc., San Rafael, CA, USA) and MeshMixer® (Autodesk Inc., San Rafael, CA, USA).

Results

Paranasal sinus tomodensitometry revealed abnormalities in shape and number. Henri IV of France suffered from sinus aplasia. Neither the left sphenoid nor left frontal sinus contrasted sharply, and a remarkable pneumatization of the right clinoid processes extended throughout the height of the right pterygoid process. The total volumes of Henri IV's mastoid air‐cells were estimated at 27 and 26 mL, respectively, for the right and left sides, exceeding the normal mean and the maximum of modern subjects by a wide margin. No sign of chronic ear or sinus condition was found.

Conclusions

An innovative method has been developed in forensic medicine to establish hypotheses about the growth and respiratory conditions of the face.
Advances in Rare Earth‐Doped ZnO Photocatalysts: Enhancing Photogenerated Electron‐Hole Pairs for Radical Atom Generation
Authors: Hasanah Andi Uswatun , Ikbal Muh. Syihab , Tahir Dahlang
Published: April 2024

Zinc oxide (ZnO) is a promising material with a diverse range of applications, spanning gas sensing, photonics, photovoltaics, energy conversion, water splitting, photocatalysis, and transparent trapping. However, ZnO limited responsiveness to visible light affected to low photogenerated electron‐hole pairs (charge), low quantum efficiency, and high recombination of charge. In this review, we are addressing innovative strategies, including incorporation rare earth elements as a trap of electron to reduce recombination charge via ZnO doping from analysis 118 referenced sources. We found that hydrothermal shows very good methods for boosting efficiency up to 100 % within 60‐min. We found that for rare‐earth metals La and Ce as a doping show highest efficiency up to 100 % within 120 min irradiations, means that efficient as a trap for reducing recombination of charge. The potential of rare earth doped ZnO will enhance photogenerated electron‐hole pairs, catalyzing the generation of radical atoms via oxidation and reduction reactions. This review encapsulates the most current findings, it serves as a valuable resource for scholars seeking to advance their understanding of rare earth doped ZnO photocatalysts and developing innovative photocatalytic technologies.
Metal‐Catalyzed Enantioselective Cleavage of Aromatic C−O Bonds
Authors: Su Yusheng , Cao Zhi‐Chao
Published: April 2024

Phenol derivatives are naturally abundant or can be easily fabricated from commercially accessible building blocks. In recent years, with the aim of producing functionally important chiral compounds in enantioenriched form, there has been initial progress in the development of metal‐catalyzed cross‐coupling reactions that involve the enantioselective cleavage of aromatic C−O bonds. This concept encompasses a review of the significant advancements in this field, as well as the associated strategies. Moreover, the challenges and potential opportunities in this area are also underscored.
Engineering Amino Acid and Peptide Supramolecular Architectures through Fluorination
Authors: Veronese Eleonora , Metrangolo Pierangelo , Dichiarante Valentina
Published: April 2024

Fluorinated non‐natural amino acids are attracting considerable research interest, especially in the biomedical field and in materials science, thanks to their ability to self‐assemble into peculiar supramolecular structures. The conformational changes induced by the presence of fluorine atoms obviously affect their functions, as well as the biological activity of the deriving peptides and proteins. Here, we will briefly describe the main effects of fluorination on the aggregation behavior of such building blocks, focusing in particular on their improved tendency to form fibrils, and gels therefrom. Our aim is to underline the promising potential of fluorination as a tool to affect the self‐assembly features of amino acids, both when used alone and when inserted into polypeptide sequences. The ability of fluorine to influence physical, chemical, and structural properties of these substrates offers the possibility to engineer bioinspired materials with specific and tunable functions.
Mimicking Ozonolysis via Mechanochemistry: Internal Alkynes to 1,2‐Diketones using H5IO6
Authors: Nayek Pravat , Mal Prasenjit
Published: April 2024

Utilizing periodic acid as an environmentally benign oxidizing agent, this study introduces a novel mechanochemical method that mimics ozonolysis to convert internal alkynes into 1,2‐diketones, showcasing effective emulation of ozone‘s reactivity. Notably, this oxidation occurs at room temperature in aerobic conditions, eliminating the need for toxic transition metals, hazardous oxidants, or expensive solvents. Through control experiments validating the mechanism, substantial evidence supports a concerted reaction pathway. This progress marks a significant stride toward cleaner and more efficient chemical synthesis, mitigating the environmental impact of conventional processes. Assessing the green chemistry metrics in both solvent‐free and previously reported solvent‐based methods, our eco‐friendly protocol demonstrates an E‐factor of 7.40, a 51.7 % atom economy, a 45.5 % atom efficiency, 100 % carbon efficiency, and 11.9 % reaction mass efficiency when solvents are not used.
Surface Functionalized Titanium Nitride Electrode for CMOS Compatible Bioelectronic Devices
Authors: Yu Meng , Tang Xiaohui , Yang Shijia , Li Zhenhua , Chen Chang , Xie Sijia
Published: April 2024

The development of bioelectronic devices is heading toward high throughput and high resolution. Yet, most electrode materials utilized in electrical biosensing are not compatible with the manufacturing techniques of semiconductor chips, which somehow hinders the integration and miniaturization of these devices. Titanium nitride (TiN) is a durable and economical material that is widely used in CMOS‐based integrated circuits, bioelectronic systems, electrocatalytic systems, etc. Considering different application scenarios, new and efficient methods are required to functionalize TiN surface. In this study, a surface functionalization approach by covalent grafting of an organic thin film containing hydroxyl groups on TiN surface via electroreduction of diazonium salt 4‐(2‐hydroxyethyl)benzenediazonium was presented. Cyclic voltammetry (CV) procedures were carried out at the potential ranges of −0.8 V~0.5 V (vs Ag/AgCl) with varying numbers of potential cycles (i. e., 5, 25, and 50 cycles) in order to study the thickness of modification layer. Then, the electrochemical property, surface morphology, and chemical structures of the sample before and after modifications were investigated via multiple characterization techniques, such as CV, atomic force microscopy (AFM), scanning electron microscope (SEM) and X‐ray photoelectron spectroscopy (XPS), etc., thereby confirming the successful grafting of hydroxyl groups onto the TiN surface. The experiments on DNA synthesis aimed to explore the potential of modified TiN electrode as a novel platform for DNA data storage applications and the corresponding proof‐of‐principle was accomplished by the process of coupling Cy3‐phosphoramidite. Finally, the experiments were successfully reproduced on the randomly selected sites of the modified TiN microarray chips demonstrating the potential of technical protocol to extend applications in future bioelectronic devices, such as bio‐sensing, high‐throughput DNA synthesis, and molecular manipulation.
Folding of the cerebellar cortex is clade‐specific in form but universal in degree
Authors: York Annaleigh R. , Sherwood Chet C. , Manger Paul R. , Kaas Jon H. , Mota Bruno , Herculano‐Houzel Suzana
Published: April 2024

Like the cerebralcortex, the surface of the cerebellum is repeatedly folded. Unlike the cerebralcortex, however, cerebellar folds are much thinner and more numerous; repeatthemselves largely along a single direction, forming accordion‐like folds transverseto the mid‐sagittal plane; and occur in all but the smallest cerebella. We haveshown previously that while the location of folds in mammalian cerebral cortex isclade‐specific, the overall degree of folding strictly follows a universalpower law relating cortical thickness and the exposed and total surface areas predictedfrom the minimization of the effective free energy of an expanding, self‐avoidingsurface of a certain thickness. Here we show that this scaling law extends tothe folding of the mid‐sagittal sections of the cerebellum of 53 speciesbelonging to six mammalian clades. Simultaneously, we show that each clade hasa previously unsuspected distinctive spatial pattern of folding evident at themid‐sagittal surface of the cerebellum. We note, however, that the mammaliancerebellum folds as a multi‐fractal object, because of the difference betweenthe outside‐in development of the cerebellar cortex around a preexisting coreof already connected white matter, compared to the inside‐out development ofthe cerebral cortex with a white matter volume that develops as the cerebralcortex itself gains neurons. We conclude that repeated folding, one of the mostrecognizable features of biology, can arise simply from the interplay betweenthe universal applicability of the physics of self‐organization and biological,phylogenetical clade‐specific contingency, without the need for invokingselective pressures in evolution.
Decarboxylative Ketonization of Aliphatic Carboxylic Acids in a Continuous Flow Reactor Catalysed by Manganese Oxide on Silica
Authors: Goebel Jonas F. , Belitz Florian , Prendes Daniel Sowa , Haver Yannik , Diehl Patrick , Muhler Martin , Gooßen Lukas J.
Published: April 2024

The sustainable synthesis of long carbon chain molecules from carbon dioxide, water and electricity relies on the development of waste‐free, highly selective C−C bond forming reactions. An example for such a power‐to‐chemicals process is the industrial‐scale fermentation for the production of hexanoic acid. Herein, we describe how this product is transformed into 6‐undecanone via decarboxylative ketonization using a heterogeneous manganese oxide/silica catalyst. The reaction reaches full conversion with near‐complete selectivity when carried out in a continuous flow reactor, requires no solvent or carrier gas, and releases carbon dioxide and water as the only by‐products. The reactor was operated for several weeks with no loss of reactivity, producing 7 kg of 6‐undecanone from 10 g of catalyst and achieving a productivity of 1.135 kg per litre of reactor volume per hour. 6‐Undecanone and other long‐chain ketones accessible this way can be hydrogenated to industrially meaningful alkanes, or converted into valuable fatty acids via a hydrogenation/elimination/isomerizing hydrocarboxylation sequence.
OMIP‐102: 50‐color phenotyping of the human immune system with in‐depth assessment of T cells and dendritic cells
Authors: Konecny Andrew J. , Mage Peter L. , Tyznik Aaron J. , Prlic Martin , Mair Florian
Published: April 2024

We report the development of an optimized 50‐color spectral flow cytometry panel designed for the in‐depth analysis of the immune system in human blood and tissues, with the goal of maximizing the amount of information that can be collected using currently available flow cytometry platforms. We established and tested this panel using peripheral blood mononuclear cells (PBMCs), but included CD45 to enable its future use for the analysis of human tissue samples. The panel contains lineage markers for all major immune cell subsets, and an extensive set of phenotyping markers focused on the activation and differentiation status of the T cell and dendritic cell (DC) compartment. We outline the biological insight that can be gained from the simultaneous measurement of such a large number of proteins and propose that this approach provides a unique opportunity for the comprehensive exploration of the immune status in human samples with a limited number of cells. Of note, we tested the panel to be compatible with cell sorting for further downstream applications. Furthermore, to facilitate the wide‐spread implementation of such a panel across different cohorts and samples, we established a trimmed‐down 45‐color version which can be used with different spectral cytometry platforms. Finally, to generate this panel, we utilized not only existing panel design guidelines, but also developed new metrics to systematically identify the optimal combination of 50 fluorochromes and evaluate fluorochrome‐specific resolution in the context of a 50‐color unmixing matrix.
In vitro and in silico investigation of FDA‐approved drugs to be repurposed against Alzheimer's disease
Authors: Akkaya Didem , Seyhan Gökçe , Sari Suat , Barut Burak
Published: April 2024

Alzheimer's disease (AD), one of the main causes of dementia, is a neurodegenerative disorder. Cholinesterase inhibitors are used in the treatment of AD, but prolonged use of these drugs can lead to serious side effects. Drug repurposing is an approach that aims to reveal the effectiveness of drugs in different diseases beyond their clinical uses. In this work, we investigated in vitro and in silico inhibitory effects of 11 different drugs on cholinesterases. The results showed that trimebutine, theophylline, and levamisole had the highest acetylcholinesterase inhibitory actions among the tested drugs, and these drugs inhibited by 68.70 ± 0.46, 53.25 ± 3.40, and 44.03 ± 1.20%, respectively at 1000 µM. In addition, these drugs are bound to acetylcholinesterase via competitive manner. Molecular modeling predicted good fitness in acetylcholinesterase active site for these drugs and possible central nervous system action for trimebutine. All of these results demonstrated that trimebutine was determined to be the drug with the highest potential for use in AD.
Size matters: Natural experiments suggest the dear enemy effect is moderated by pack size in African wild dogs
Authors: Claase Megan J. , Cherry Mike I. , McNutt J. Weldon , Apps Peter J. , Jordan Neil R.
Published: April 2024

Remote monitoring of communal marking sites, or latrines, provides a unique opportunity to observe undisturbed scent marking behaviour of African wild dogs (Lycaon pictus). We used remote camera trap observations in a natural experiment to test behavioural scent mark responses to rivals (either familiar neighbours or unfamiliar strangers), to determine whether wild dogs exhibit the “dear enemy” or “nasty neighbour” response. Given that larger groups of wild dogs represent a greater threat to smaller groups, including for established residents, we predicted that the overarching categories “dear enemy” vs. “nasty neighbour” may be confounded by varying social statuses that exists between individual dyads interacting. Using the number of overmarks as a metric, results revealed an interaction between sender and receiver group size irrespective of familiarity consistent with this prediction: in general, individuals from large resident packs overmarked large groups more than they overmarked smaller groups, whereas individuals from smaller packs avoided overmarking larger groups, possibly to avoid detection. Monitoring a natural system highlights variables such as pack size that may be either overlooked or controlled during scent presentation experiments, influencing our ability to gain insights into the factors determining territorial responses to rivals.
Quantifying the roles of climate, herbivory, topography, and vegetation on tree establishment in the treeline ecotone
Authors: Mienna Ida M. , Klanderud Kari , Næsset Erik , Gobakken Terje , Bollandsås Ole Martin
Published: April 2024

The transition zone between the upper forest boundary and the treeless alpine vegetation (i.e., the treeline ecotone) is expected to shift upward in elevation with global warming. Multiple factors in addition to climate are influencing tree establishment, but it is uncertain to what degree. In this study, we took advantage of a unique dataset with field measurements of mountain birch trees acquired from 32 boreal–alpine treeline ecotone sites situated along a 1100‐km latitudinal gradient in Norway to investigate the role of climate, herbivory, topography, and vegetation on the establishment success of trees. To represent tree establishment, we recorded occurrence, survival, and height growth of short juvenile birch trees (stem height ≤1 m) as response variables at each site in 2008, 2012, and 2018. We used already available climate and herbivory data, and airborne laser scanning (ALS) and unmanned aerial vehicle (UAV) surveyed imagery together with field measurements to compute topography and vegetation explanatory variables per site on microsite scale (approx. 1 m2). We observed a clear decrease in short juvenile birch tree establishment due to livestock herbivory, evidenced by lower occurrence, reduced survival rate, and diminished height growth in treeline ecotones with higher livestock densities. Winter precipitation and the two land cover classes, tree‐covered area and lee side vegetation, were also important for tree establishment. However, the direction and magnitude of the relationships depended on the stage of establishment. While winter precipitation can lead to higher tree occurrence, long‐term survival is not necessarily ensured, reflecting diverse requirements for optimal conditions of tree establishment. Thus, our results show that occurrence, survival, and height growth of short juvenile birch trees differ in their requirements to climate, topography, and vegetation, but tree establishment is consistently low with livestock herbivory. Overall, our results suggest that treeline ecotones will shift toward higher elevations in areas with little or no livestock herbivory and close to already established trees and in lee sides. Regarding management and conservation issues, our results suggest that free‐roaming livestock can reduce tree establishment and hinder treeline ecotone shifts into threatened alpine ecosystems, at least for birch‐dominated treelines.
Tiny niche terrain induces gully headcut retreat
Authors: Wang Chao , Cai Chongfa , Deng Yusong
Published: April 2024

Gully erosion damages land resources and endangers human productivity and life, making it a key issue in global research on soil erosion nowadays. Gully headcut retreat (GHR) is the main form of gully erosion. Tiny concave features can be found in many retreating gully heads worldwide, and they are referred to as “niche terrain” in this study. To investigate the association between niche terrain and GHR, relevant research was reviewed on niches and stability analysis of gully heads with niches was modelled and analysed. Studies have shown that not all niches worldwide are identical due to regional differences in internal material–external environmental conditions. Special soil properties, joints, and cracks are the internal material conditions that lead to the formation of niche. External conditions include climate conditions, vegetation conditions, and topography. Water is the driving force for the formation of niche, while vegetation and topography are key factors. Niches can be regarded as the initial stage of GHR in areas where gully erosion is intense. In general, GHR is a composite cyclical process dominated by hydraulic erosion in the early stage and gravitational erosion in the late stage, including niche formation, inward concave formation, free face formation, overhanging soil collapse, and niche reformation. In this study, a model of gully head stability is applied, and it is found that the stability‐based factor of safety decreases exponentially with increasing niche height and crack depth, increases exponentially with increasing niche angle, and decreases quadratically with increasing catchment slope. Summarizing the common characteristics of niche terrains worldwide can facilitate the study of the evolution of gully erosion globally.
Shedding light on imaging safety: Decoding the origin of photocytotoxicity in RhB‐assisted fluorescence imaging
Authors: Luo Chaoqun , Yao Weiyun , Zhang Haolin , Jia Mingxuan , Lim Chang‐Keun , Hu Wenbo
Published: April 2024

Photocytotoxicity represents a significant limitation in the application of dye‐assisted fluorescence imaging (FI), often resulting in undesirable cellular damage or even cell death, thereby restricting their practical utility. The prevalence of Rhodamine B (RhB) in FI underscores the importance of elucidating its photocytotoxicity effects to minimize photodamage. This study identifies the primary cause of photocytotoxicity stems from the generation of cytotoxic singlet oxygen in RhB, utilizing femtosecond transient absorption spectroscopy coupled with quantum chemical calculations. The Laser power‐dependent cellular viability reveals a threshold at about 50 mW cm−2, surpassing which produces pronounced photocytotoxicity in vitro and in vivo. Notably, this threshold significantly falls below the safety limits (<200 mW cm−2) for laser use in health care, implying a huge risk of photodamage. This study provides valuable insights into the photocytotoxicity and offers essential guidelines for developing safer imaging protocols.
Do ECB's rate hikes have spillover effects on the Hungarian BUBOR and the EUR/HUF exchange rate? A five‐variable VAR model approach using the Diebold‐Yilmaz spillover table
Authors: Albert Molnar , Ágnes Csiszárik‐Kocsír
Published: April 2024

We intend to show the directional volatility spillovers between the European short term interbank lending rates (3‐month Euro Interbank Offered Rate [EURIBOR] and Euro Short‐Term Rate [ESTR]) and the Hungarian Budapest Interbank Offered Rate (BUBOR) and Euro‐Hungarian Forint exchange rate. To determine the extent to which the variables affect each other's volatilities we build a five‐variable vector autoregression (VAR) and determine the spillover table like in Diebold‐Yilmaz's 2012 work. This methodology is preferred to a simple impulse response function (IRF) because we manage to avoid the problem of non‐orthogonal innovations via the generalized forecast error variance decomposition framework. The issue of variable ordering, therefore, does not arise. We focus on three episodes of increased volatility in Hungarian and European short‐term interest rates: Q3–Q4 of 2019, Q1 of 2020 and Q3 of 2022. These episodes correspond to volatility spikes in EU markets that to some extent had a measurable spillover effect on Hungarian interbank rates. We find that on average, across the entire sample of 957 observations, about 6.3% of the volatility forecast error variance in all five European and Hungarian variables comes from spillovers. The total and directional spillovers over the sample are extremely low. We conclude that the European Central Bank's surprise policy decisions have a marginal impact on Hungarian interbank rates. We also find that BUBOR is primarily a net receiver of spillovers from the MAX short‐term government bond benchmark rather than the EURIBOR—this disproved our initial considerations.
Financial inclusion in India: How far do grassroots institutions matter?
Authors: Saravanabhavan Shika , Rajeev Meenakshi
Published: April 2024

Though the relevance of grassroots institutions for financial inclusion (FI) is widely recognised, we still do not fully understand its differential effect on FI, particularly in relation to commercial banks. To investigate this issue, we consider the household's moneylender dependence as an indicator of financial exclusion and thus our outcome variable. Further, we have developed FI indices using indicators of commercial and cooperative banks, which we used as explanatory variables in our analysis. Our results show that, while there is a decreased dependence on moneylenders even at low levels of FI through cooperatives, commercial banks show an inverted U‐shaped relationship implying a decreasing effect only after a threshold level.
What do brain oscillations tell about the human sense of smell?
Authors: Mignot Coralie , Weise Susanne , Podlesek Dino , Leonhardt Georg , Bensafi Moustafa , Hummel Thomas
Published: April 2024

Brain activity may manifest itself as oscillations which are repetitive rhythms of neuronal firing. These local field potentials can be measured via intracranial electroencephalography (iEEG). This review focuses on iEEG used to map human brain structures involved in olfaction. After presenting the methodology of the review, a summary of the brain structures involved in olfaction is given, followed by a review of the literature on human olfactory oscillations in different contexts. A single case is provided as an illustration of the olfactory oscillations. Overall, the timing and sequence of oscillations found in the different structures of the olfactory system seem to play an important role for olfactory perception.
Cognitive profiles of strategic decision‐makers: Implications for exploration–exploitation strategies
Authors: Vlašić Goran , Dabić Marina , Krupka Zoran
Published: April 2024

Organizational ambidexterity has long been in the focus of understanding how organizations address tensions between exploitation, which implies building new competencies in order to drive radical change, and exploitation, which implies building on top of existing competencies in order to deliver persistent incremental improvements. Research has shown that, at the organizational level, established incumbent organizations tend to avoid exploration. In this paper, we focus on understanding which cognitive profiles tend to get promoted to the highest management positions in established incumbent organizations. To address this research question, we used a data set on 176 key decision‐makers at five multinational organizations. Results indicate that inherent biases in promotion decisions at the highest levels of the established incumbent organizations favor pattern‐recognition cognitive profiles of managers, thus influencing organizational preference for exploitation over exploration. Results have implications for theory, explaining neurocognitive underpinnings of preference for exploitation in case of established incumbent organizations which arise from biases in promotional decisions; and for practice, implying the importance of debiasing promotion decisions to ensure organizational ability to deliver on explorative strategies, favoring innovations and new market creation.