bluuebunny/crossref_metadata_2025 huggingface dataset:
Selective electrooxidation glycerol to lactic acid coupled with hydrogen production over a cooperative BiOx/Au catalyst
Authors: Yan Yifan , Hao Pengjie , Fu Yu , Chen Wangsong , Shi Qiwei , Zhou Hua , Kong Xianggui , Li Zhenhua , Shao Mingfei , Duan Xue
Published: January 2024

Utilizing sustainable electrocatalysis to upcycle glycerol (GLY; the by‐product of biodiesel) to lactic acid (LA; the key monomers for biodegradable polymer) is an efficient way to reduce the cost of biodiesel, which is also consistent with the waste‐to‐wealth principle. However, current research still suffers from issues of low LA selectivity (<80%), especially at high current density. Herein, we designed a cooperative catalyst by modifying BiOx nanolayers on gold nanoparticles (BiOx/Au), achieving high LA selectivity (82%) at high current density (226 mA cm−2 at 1.05 V vs. RHE), outperforming most of the reported works in the literature. We reveal that BiOx could promote the adsorption of the middle hydroxyl of GLY, which facilitates the formation of DHA and thus enables high LA selectivity. Moreover, the electron‐deficient Au in BiOx/Au is responsible for the enhanced current density, which is more beneficial to generate reactive oxygen species (OH*). To further reveal the application potential of this electrocatalytic strategy, we realized that the conversion of crude GLY extracted from cooking oil to LA coupled with H2 production using a membrane‐free flow electrolyzer, demonstrating a sustainable fashion to convert biodiesel waste into high value‐added product and H2 fuel.
Compliance with the 24‐h movement behaviors guidelines among urban and rural Brazilian preschoolers
Authors: Martins Clarice , Mota Jéssica , Goulart Natália , Silva Morgana , Silva Tamires , Carvalho Ferdinando , Mota Jorge , Bandeira Paulo Felipe , Lemos Luís
Published: January 2024

Background

The importance of movement behaviors for health is well‐known, although few studies have examined the compliance with movement guidelines in preschoolers from different living contexts. This study reported the compliance with the 24‐h movement behaviors guidelines among low‐income Brazilian preschoolers from rural and urban areas, according to age.

Methods

A total of 453 preschoolers (n = 222 urban), aged between 3 and 5 years, provided physical activity (PA) data (Actigraph wGT3X). Sleep duration, and screen time were parent‐reported. Preschoolers were classified as compliant/non‐ compliant with the 24‐h movement guidelines, according to age. The association between prevalence of compliance with the recommendations and the children's living setting were estimated (SPSS; 27.0).

Results

Preschoolers were active (mean = 299.19 ± 76.42; and 369.76 ± 95.56 min/day in urban and rural areas, respectively), though moderate‐to‐vigorous physical activity (MVPA) time was below the 60 daily minutes recommended in both urban and rural settings (mean = 38.39 ± 21.36; and 47.32 ± 24.28, respectively). None of the urban children complied with the three recommendations simultaneously, while in the rural area, only 2.6% were compliant. Single movement behaviors compliances in the urban setting were 6.8%, 28.8% and 5.4% for PA, sleep, and screen time, respectively; while for rural settings were 16.5%, 21.2%, and 7.4%. Living in the rural area was related to the compliance with PA recommendation for the 5‐year‐old preschoolers.

Conclusion

In both urban and rural Brazilian areas, very few preschoolers are compliant with the guidelines, and more than one third of the children do not comply with any of the recommendations. Strategies and programs to promote compliance with movement behaviors guidelines should consider children's living setting and their age groups.
Synthesis and Photophysical Evaluation of Dialkynyl‐N‐(het)arylpyrroles: Promising Key Compounds in Fluorescence Chemistry
Authors: Peglow Thiago J. , Nobre Patrick C. , Thomaz João Pedro S. S. C. , Vieira Marcelo M. , Junior Henrique C. S. , Dalberto Bianca T. , Schneider Paulo H. , Rodembusch Fabiano S. , Nascimento Vanessa
Published: January 2024

In this work, we present a series of chromophores based on dialkynyl‐N‐(het)arylpyrrole, featuring diverse combinations of donor‐acceptor moieties. The study explores the potential of fluorophores derived from (alkynyl)arylpyrroles, investigating the impact of the central core‘s nature with phenyl and pyridyl groups, along with various arylethynyl groups. Additionally, we assess these derivatives in the selective synthesis of non‐symmetrical ullazine derivatives with broad photophysical potential through photocatalysis. The precursors exhibit absorption maxima in the UVB region (~300 nm), while the model mono‐ullazine displays absorption maxima in the UVA region (~320 nm). Emission maxima for the precursors are observed between the UVA and violet regions, with the emission wavelength tailored by the substituents. In contrast, the mono‐ullazine fluoresces in the blue region. Remarkably, selected compounds exhibit an intricate photophysical behavior where a dual fluorescence emission with a large Stokes shift was present, which could not be clearly related to an intramolecular charge transfer (ICT) mechanism. Theoretical calculations support the experimental findings.
Behaviour support provision in Australia: A cross‐sectional survey of practitioners developing behaviour intervention plans
Authors: Kelly Glenn , Kremer Peter , Louise Kymberly , Fisher Alinka
Published: January 2024

There is currently a limited understanding of the characteristics of the workforce of behaviour support practitioners in Australia. A better understanding will help future considerations of training requirements, professional credentialling and associated professional regulation. A cross‐sectional online survey captured the demographic and work‐related characteristics of those who develop behaviour intervention plans for people with disability in Australia. The sample (n = 423) was primarily female (78 per cent), aged 26–45 years (57 per cent) and held a graduate (39 per cent) or postgraduate (53 per cent) degree. The largest single professional group was psychologists (28 per cent). The most common duration of experience was 1 year. Approximately half of the respondents were allied health practitioners either registered with the Australian Health Practitioner Regulation Agency or a member of the National Alliance of Self‐Regulating Health Professionals. The majority of practitioners had registered with the National Disability Insurance Scheme to provide behaviour support services (85 per cent). Both clients and services were concentrated in metropolitan regions, raising concerns regarding equity of access to behaviour support in remote communities, and among Aboriginal and Torres Strait Islanders. Given the vulnerability of many people with disabilities in receipt of behaviour support, ongoing policy and procedure work is needed to ensure professional credentialling and regulation of the workforce.
Cutting more than meals: Increasing severity of food insecurity is associated with the number and types of household financial strategies used to cope with inflation
Authors: Seivwright Ami , Kocar Sebastian , Visentin Denis , Kent Katherine
Published: January 2024

Food insecurity is a prominent social determinant of health. There is evidence of increasing food insecurity in high‐income countries amid inflationary pressures. Yet, we know relatively little about the strategies that people employ to manage food insecurity nor how the severity of food insecurity affects the use of these strategies. Accordingly, this study of a nonprobability convenience online panel sample of 1284 adults in Tasmania assessed food insecurity and the strategies undertaken to manage rising costs of living. Structural equation modelling of 51 financial management actions revealed five strategies: reducing food quantity and quality, reducing housing and transport costs, drawing on assets, savings and credit, reducing insurance costs and reducing discretionary expenditure. Generalised linear regression modelling demonstrated that the use of coping strategies increased significantly with each categorical increase in food insecurity for each strategy except reducing insurance costs, in which increases became significant at moderate food insecurity. Overall, the results suggest that those experiencing food insecurity are also sacrificing in other areas, which is likely to have immediate and longer‐term effects on health, social and financial wellbeing. Opportunities to mitigate these consequences, including strengthening of social safety nets, nutrition programmes and structural investment to ensure universal access to food, are discussed.
Rhodium‐Catalyzed One‐Carbon Ring Expansion of Aziridines with Vinyl‐N‐triftosylhydrazones for the Synthesis of 2‐Vinyl Azetidines
Authors: Ning Yongquan , Chen Hongzhu , Ning Yongyue , Zhang Jin , Bi Xihe
Published: January 2024

Azetidines, being four‐membered N‐heterocycles, possess significant potential in contemporary medicinal chemistry owing to their favorable pharmacokinetic properties. Regrettably, the incorporation of functionalized azetidines into pharmaceutical lead structures has been impeded by the absence of efficient synthetic methods for their synthesis. In this study, a Rh‐catalyzed one‐carbon ring expansion of aziridines with vinyl‐N‐triftosylhydrazones is presented, which facilitates the synthesis of high value‐added 2‐alkenyl azetidine products. This research represents the first example of ring expansion of aziridines enabled by vinyl carbenes. Additionally, a one‐pot two‐step protocol, initiated from cinnamaldehyde, was successfully achieved, offering a step‐economical and facile approach for the synthesis of these compounds. The pivotal aspect of this successful transformation lies in the in situ formation of an alkenyl aziridinium ylide intermediate. Experimental investigations, coupled with computational studies, suggest that a diradical pathway is involved in the reaction mechanism.
Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes
Authors: Fernandes Anthony J. , Giri Rahul , Houk Kendall N. , Katayev Dmitry
Published: January 2024

We highlight key contributions in the field of direct radical CAr− H (hetero)aromatic functionalization involving fluorinated radicals. A compilation of Functional Group Transfer Reagents and their diverse activation mechanisms leading to the release of radicals are discussed. The substrate scope for each radical is analyzed and classified into three categories according to the electronic properties of the substrates. Density functional theory computational analysis provides insights into the chemical reactivity of several fluorinated radicals through their electrophilicity and nucleophilicity parameters. Theoretical analysis of their reduction potentials also highlights the remarkable correlation between electrophilicity and oxidizing ability. It is also established that highly fluorinated radicals (e.g. ⋅OCF3) are capable of engaging in single‐electron transfer (SET) processes rather than radical addition, which is in good agreement with experimental literature data. A reactivity scale, based on activation barrier of addition of these radicals to benzene is also elaborated using the high accuracy DLPNO‐(U)CCSD(T) method.
Evolved Readers of 5‐Carboxylcytosine CpG Dyads Reveal a High Versatility of the Methyl‐CpG‐Binding Domain for Recognition of Noncanonical Epigenetic Marks
Authors: Kosel Brinja , Bigler Katrin , Buchmuller Benjamin C. , Acharyya Suchandra R. , Linser Rasmus , Summerer Daniel
Published: January 2024

Mammalian genomes are regulated by epigenetic cytosine (C) modifications in palindromic CpG dyads. Including canonical cytosine 5‐methylation (mC), a total of four different 5‐modifications can theoretically co‐exist in the two strands of a CpG, giving rise to a complex array of combinatorial marks with unique regulatory potentials. While tailored readers for individual marks could serve as versatile tools to study their functions, it has been unclear whether a natural protein scaffold would allow selective recognition of marks that vastly differ from canonical, symmetrically methylated CpGs. We conduct directed evolution experiments to generate readers of 5‐carboxylcytosine (caC) dyads based on the methyl‐CpG‐binding domain (MBD), the widely conserved natural reader of mC. Despite the stark steric and chemical differences to mC, we discover highly selective, low nanomolar binders of symmetric and asymmetric caC‐dyads. Together with mutational and modelling studies, our findings reveal a striking evolutionary flexibility of the MBD scaffold, allowing it to completely abandon its conserved mC recognition mode in favour of noncanonical dyad recognition, highlighting its potential for epigenetic reader design.
Development and Applications of D‐Amino Acid Derivatives‐based Metabolic Labeling of Bacterial Peptidoglycan
Authors: Zheng Yongfang , Zhu Xinyu , Jiang Mingyi , Cao Fangfang , You Qing , Chen Xiaoyuan
Published: January 2024

Peptidoglycan, an essential component within the cell walls of virtually all bacteria, is composed of glycan strands linked by stem peptides that contain D‐amino acids. The peptidoglycan biosynthesis machinery exhibits high tolerance to various D‐amino acid derivatives. D‐amino acid derivatives with different functionalities can thus be specifically incorporated into and label the peptidoglycan of bacteria, but not the host mammalian cells. This metabolic labeling strategy is highly selective, highly biocompatible, and broadly applicable, which has been utilized in various fields. This review introduces the metabolic labeling strategies of peptidoglycan by using D‐amino acid derivatives, including one‐step and two‐step strategies. In addition, we emphasize the various applications of D‐amino acid derivative‐based metabolic labeling, including bacterial peptidoglycan visualization (existence, biosynthesis, and dynamics, etc.), bacterial visualization (including bacterial imaging and visualization of growth and division, metabolic activity, antibiotic susceptibility, etc.), pathogenic bacteria‐targeted diagnostics and treatment (positron emission tomography (PET) imaging, photodynamic therapy, photothermal therapy, gas therapy, immunotherapy, etc.), and live bacteria‐based therapy. Finally, a summary of this metabolic labeling and an outlook is provided.
Deciphering Structure‐Activity Relationship Towards CO2 Electroreduction over SnO2 by A Standard Research Paradigm
Authors: Guo Zhongyuan , Yu Yihong , Li Congcong , Campos dos Santos Egon , Wang Tianyi , Li Huihui , Xu Jiang , Liu Chuangwei , Li Hao
Published: January 2024

Authentic surface structures under reaction conditions determine the activity and selectivity of electrocatalysts, therefore, the knowledge of the structure‐activity relationship can facilitate the design of efficient catalyst structures for specific reactivity requirements. However, understanding the relationship between a more realistic active surface and its performance is challenging due to the complicated interface microenvironment in electrocatalysis. Herein, we proposed a standard research paradigm to effectively decipher the structure‐activity relationship in electrocatalysis, which is exemplified in the CO2 electroreduction over SnO2. The proposed practice has aided in discovering authentic/resting surface states (Sn layer) of SnO2 accountable for the electrochemical CO2 reduction reaction (CO2RR) performance under electrocatalytic conditions, which then is corroborated in the subsequent CO2RR experiments over SnO2 with different morphologies (nanorods, nanoparticles, and nanosheets) in combination with in situ characterizations. This proposed methodology is further extended to the SnO electrocatalysts, providing helpful insights into catalytic structures. It is believed that our proposed standard research paradigm is also applicable to other electrocatalytic systems, in the meantime, decreases the discrepancy between theory and experiments, and accelerates the design of catalyst structures that achieve sustainable performance for energy conversion.
Engineering Co‐N‐Cr Cross‐Interfacial Electron Bridges to Break Activity‐Stability Trade‐Off for Superdurable Bifunctional Single Atom Oxygen Electrocatalysts
Authors: Zhang Yun‐Long , Liu Bo , Dai Yun‐Kun , Shen Li‐Xiao , Guo Pan , Xia Yun‐Fei , Zhang Ziyu , Kong Fantao , Zhao Lei , Wang Zhen‐Bo
Published: January 2024

Atomically dispersed metal‐nitrogen‐carbon (M‐N‐C) catalysts have exhibited encouraging oxygen reduction reaction (ORR) activity. Nevertheless, the insufficient long‐term stability remains a widespread concern owing to the inevitable 2‐electron byproducts, H2O2. Here, we construct Co‐N‐Cr cross‐interfacial electron bridges (CIEBs) via the interfacial electronic coupling between Cr2O3 and Co‐N‐C, breaking the activity‐stability trade‐off. The partially occupied Cr 3d‐orbitals of Co‐N‐Cr CIEBs induce the electron rearrangement of CoN4 sites, lowering the Co‐OOH* antibonding orbital occupancy and accelerating the adsorption of intermediates. Consequently, the Co‐N‐Cr CIEBs suppress the two‐electron ORR process and approach the apex of Sabatier volcano plot for four‐electron pathway simultaneously. As a proof‐of‐concept, the Co‐N‐Cr CIEBs is synthesized by the molten salt template method, exhibiting dominant 4‐electron selectively and extremely low H2O2 yield confirmed by Damjanovic kinetic analysis. The Co‐N‐Cr CIEBs demonstrates impressive bifunctional oxygen catalytic activity (▵E=0.70 V) and breakthrough durability including 100 % current retention after 10 h continuous operation and cycling performance over 1500 h for Zn‐air battery. The hybrid interfacial configuration and the understanding of the electronic coupling mechanism reported here could shed new light on the design of superdurable M‐N‐C catalysts.
Site‐Selective Photo‐Crosslinking of Stilbene Pairs in a DNA Duplex Mediated by Ruthenium Photocatalyst
Authors: Kashida Hiromu , Azuma Hidenori , Sotome Hikaru , Miyasaka Hiroshi , Asanuma Hiroyuki
Published: January 2024

We herein report a method for site‐selective photo‐crosslinking of a DNA duplex. A stilbene pair was introduced into a DNA duplex and a ruthenium complex was conjugated with a triplex‐forming oligonucleotide. We demonstrated that [2+2] photocycloaddition of the stilbene pair occurred upon irradiation with visible light when the ruthenium complex was in close proximity due to triplex formation. No reaction occurred when the ruthenium complex was not in proximity to the stilbene pair. The wavelength of visible light used was of lower energy than the wavelength of UV light necessary for direct excitation of stilbene. Quantum chemical calculation indicated that ruthenium complex catalyzed the photocycloaddition via triplet‐triplet energy transfer. Site selectivity of this photo‐crosslinking system was evaluated using a DNA duplex bearing two stilbene pairs as a substrate; we showed that the site of crosslinking was precisely regulated by the sequence of the oligonucleotide linked to the ruthenium complex. Since this method does not require orthogonal photoresponsive molecules, it will be useful in construction of complex photoresponsive DNA circuits, nanodevices and biological tools.
N‐Terminal‐Specific Dual Modification of Peptides through Copper‐Catalyzed [3+2] Cycloaddition
Authors: Machida Haruka , Kanemoto Kazuya
Published: January 2024

Site‐specific introduction of multiple components into peptides is greatly needed for the preparation of densely functionalized and structurally uniform peptides. In this regard, N‐terminal‐specific peptide modification is attractive, but it can be difficult due to the presence of highly nucleophilic lysine ϵ‐amine. In this work, we developed a method for the N‐terminal‐specific dual modification of peptides through a three‐component [3+2] cycloaddition with aldehydes and maleimides under mild copper catalysis. This approach enables exclusive functionalization at the glycine N‐terminus of iminopeptides, regardless of the presence of lysine ϵ‐amine, thus affording the cycloadducts in excellent yields. Tolerating a broad range of functional groups and molecules, the present method provides the opportunity to rapidly construct doubly functionalized peptides using readily accessible aldehyde and maleimide modules.
Boron‐polymer composites engineered for compression molding, foaming, and additive manufacturing
Authors: Stockdale John R. , Legett Shelbie A. , Torres Xavier M. , Pacheco Adam , Adhikari Santosh , Bezek Lindsey , Labouriau Andrea
Published: January 2024

Boron (specifically 10B) is the element of choice to shield thermal neutrons due to its large (n, α) cross‐section; however, very few polymer composites containing high boron concentrations are available. This study aimed to determine the maximum possible amount of boron that could be introduced into a polymer matrix. Diverse manufacturing techniques, ranging from additive manufacturing to compression molding, were employed to fabricate inks and filaments for 3D printing, foams, and flexible pads. Composites using siloxanes, poly(lactic acid), and acrylonitrile butadiene styrene containing up to 80 wt% boron were sucessufully fabricated. The addition of known plasticizers (polyethylene glycol) and reinforcing agents (carbon nanofibers and fumed silica) helped to overcome fabrication problems such as clogging of the printing nozzle or crumbling of compression molded parts. In addition, the thermal‐mechanical properties of these novel boron composites were determined and shown to vary according to boron concentration, presence of additives, and fabrication techniques utilized.
Spontaneous Electric Polarization in Graphene Polytypes
Authors: Atri Simon Salleh , Cao Wei , Alon Bar , Roy Nirmal , Stern Maayan Vizner , Falko Vladimir , Goldstein Moshe , Kronik Leeor , Urbakh Michael , Hod Oded , Ben Shalom Moshe
Published: January 2024

Spontaneous electric polarization is recently observed in multilayered van der Waals stacked materials, arising from a symmetry breaking in a unit cell with two or more constituent species, or non‐centrosymmetric intra‐layer atom displacement in single‐atom‐species materials. Here, it is shown that even elemental crystals, consisting of one type of atom and composed of non‐polar and centrosymmetric layers, exhibit electric polarization if arranged in an appropriate three‐dimensional  architecture. This concept is demonstrated here for mixed‐stacking tetra‐layer polytypes of non‐polar graphene sheets. Surprisingly, it is find that the room temperature out‐of‐plane electric polarization increases with external electrostatic hole doping, rather than decreases with it owing to screening. Using first‐principles calculations, as well as a self‐consistent tight‐binding model, the emergence of polarization is explain in terms of inter‐layer charge rearrangement and the doping dependence in terms of gating‐induced inter‐layer charge transfer. This newly discovered intrinsic polarization may therefore offer new venues for designing the electronic response of graphene‐based polytypes to external fields.
Skull anatomy and paleoneurology of a new traversodontid from the Middle‐Late Triassic of Brazil
Authors: Kerber Leonardo , Roese‐Miron Lívia , Medina Thais G. M. , da Roberto‐da‐Silva Lúcio , Cabreira Sérgio F. , Pretto Flávio A.
Published: January 2024

Traversodontidae, a clade of gomphodont cynodonts, thrived during the Middle and Late Triassic, displaying a wide geographical distribution. During fieldwork in 2009, a new specimen was discovered in Ladinian/early Carnian stratigraphic layers in southern Brazil. Here, we describe this specimen and propose a new taxon closely related to Traversodon stahleckeri (Traversodontinae) but displaying a unique combination of traits (e.g., presence of a poorly developed suborbital process, mesiodistal length of the paracanine fossa similar to the length of the canine, short diastema between the fourth incisor and the upper canine, and coronoid process not entirely covering the distalmost lower postcanine). Furthermore, the endocranial anatomy of the new taxon was examined. The reconstruction of the cranial endocast revealed paleoneurological features consistent with non‐Gomphodontosuchinae traversodontids. These features include the presence of a pineal body (but the absence of an open parietal foramen). These recent findings contribute significantly to our understanding of the evolutionary history and cranial anatomy of Middle‐Late Triassic traversodontids, shedding light on the diversity and adaptations of non‐mammaliaform cynodonts.
Evolution of postcanine complexity in Gomphodontia (Therapsida: Cynodontia)
Authors: Hendrickx Christophe , Abdala Fernando , Filippini Florencia S. , Wills Simon , Benson Roger , Choiniere Jonah N.
Published: January 2024

Gomphodonts form a Triassic radiation of small to medium‐bodied (<0.5–2.5 m in length) quadrupedal cynodonts characterized by labiolingually expanded gomphodont postcanines. They were the dominant cynodont group in Middle and Late Triassic ecosystems from the Southern Hemisphere and the first predominantly herbivorous cynodonts to evolve. Gomphodonts were also the first therapsids to develop hypsodonty and a dentition with complex occlusal patterns, and their highly diagnostic upper and lower postcanines show many different morphologies. Here, we explored dental complexity in gomphodont cynodonts through time using geographic information system analysis and orientation patch count applied on 3D crown surfaces of upper and lower gomphodont postcanines belonging to 32 gomphodont taxa. This study reveals that the peak in postcanine complexity was reached early in the evolution of gomphodonts with the emergence in the Early Triassic of omnivorous or insectivorous forms with postcanines made of well‐separated cusps and cingular cuspules. Traversodontids evolved simpler postcanines via coalescence of cusps into crests and the development of large occlusal basins, and the Middle Triassic radiation of traversodontids led to a sharp decrease in mean postcanine complexity. Simplification of the postcanines in traversodontids is interpreted as being related to a gradual increase in the consumption of plant material. Interestingly, the trend of insectivory/omnivory high postcanine complexity and herbivory low dental complexity in gomphodonts is opposite to the trend of dental complexity reported in some extant mammals, with omnivorous having low dental complexity and herbivorous higher. Postcanine complexity remained relatively stable throughout the evolution of traversodontids and only slightly diminished in the Late Triassic due to the presence of minute forms with particularly simple postcanines in the Rhaetian. The major phylogenetic diversity and taxonomic richness of Gomphodontia are represented in two periods of time: at the end of the Anisian, an age in which the postcanine complexity is simplifying, and at the early Carnian when the postcanine complexity in traversodontids, the only Gomphodontia represented, is stable.
Macroscopic differences in adult human femora are linked to body mass index
Authors: Sylvester Adam D. , Zbijewski Wojciech , Shi Gengxin , Meckel Lauren A. , Chu Elaine Y. , Cunningham Deborah L. , Wescott Daniel J.
Published: January 2024

Bone functional adaptation is routinely invoked to interpret skeletal morphology despite ongoing debate regarding the limits of the bone response to mechanical stimuli. The wide variation in human body mass presents an opportunity to explore the relationship between mechanical load and skeletal response in weight‐bearing elements. Here, we examine variation in femoral macroscopic morphology as a function of body mass index (BMI), which is used as a metric of load history. A sample of 80 femora (40 female; 40 male) from recent modern humans was selected from the Texas State University Donated Skeletal Collection. Femora were imaged using x‐ray computed tomography (voxel size ~0.5 mm), and segmented to produce surface models. Landmark‐based geometric morphometric analyses based on the Coherent Point Drift algorithm were conducted to quantify shape. Principal components analyses were used to summarize shape variation, and component scores were regressed on BMI. Within the male sample, increased BMI was associated with a mediolaterally expanded femoral shaft, as well as increased neck‐shaft angle and decreased femoral neck anteversion angle. No statistically significant relationships between shape and BMI were found in the female sample. While mechanical stimulus has traditionally been applied to changes in long bong diaphyseal shape it appears that bone functional adaptation may also result in fundamental changes in the shape of skeletal elements.
Analysis of genes specific to the early maturation stage of Sesamum indicum seeds by subtraction method*,**
Authors: Okuno Yu , Kishikawa Akihiro , Imakouji Hisashi , Yoshida Motonobu
Published: January 2024

The mechanisms regulating the content ratio of unsaturated fatty acid in sesame oil need to be clarified in order to breed novel varieties with high contents of unsaturated fatty acids. Full‐length cDNA libraries prepared from sesame seeds 1 to 3 weeks after flowering were subtracted with cDNAs from plantlets of 4 weeks after germination. A total of 1545 cDNA clones was sequenced. The functions of novel genes expressed specifically during the early maturation of sesame seeds were investigated by the transformation of Arabidopsis thaliana. Thirteen genes for a transcription factor were identified, four of which were involved in ethylene signaling. Fifty‐nine genes, including those for the aquaporin‐like protein and ethylene response factor, were analyzed by overexpression in A. thaliana. The overexpression of novel genes and the aquaporin‐like protein gene in A. thaliana increased the content of unsaturated fatty acids. The localization of these products was investigated by the induction of the expression vectors for the GFP fusion protein into onion epidermal cells and sesame root cells with a particle gun. As a result, two cDNA clones were identified as good candidate genes to clarify the regulation in the yield and the ratio of unsaturated fatty acids in sesame seeds. Sein60414 (Accession No. LC603128), an intrinsic membrane protein, may be involved in the increase of unsaturated fatty acids, and Sein61074 (Accession No. LC709278) MAP3K δ‐1 protein kinase in the regulation of the total ratio of unsaturated fatty acids in sesame seeds.
Supporting teacher judgement and decision‐making: Using focused analysis to help teachers see students, learning, and quality in assessment data
Authors: Wyatt‐Smith Claire , Adie Lenore , Harris Lois
Published: January 2024

This paper reports results from an Australian study into how teachers see features of quality in student work and connect these to next‐step teaching. Data were drawn from a national 3 year project investigating teacher judgement using A–E standards. The project developed scaled exemplars of authentic student written performance assessments to support teacher judgement and inform next‐step teaching and learning. Fifty‐seven participants created evaluative explanations of grading decisions (i.e. cognitive commentaries), wrote reflective responses and participated in online meeting discussions of their cognitive commentaries. These data were examined using qualitative content and thematic analyses. Findings highlighted how stated standards influence teachers’ judgements of student work. Variation was evident in teachers’ focus on (1) content (i.e. core skills vs. extended thinking), (2) specificity of improvement points and suggested teaching strategies and (3) the connection between identified areas for improvement and teaching strategies. Most teachers were able to identify specific points for improvement. However, in the main, they selected next‐step teaching strategies that were general rather than targeted and specific. Teachers reflected that structured analysis helped direct their thinking and judgements, targeting attention on next‐step teaching. The results suggested that teacher education and professional development should focus on supporting teachers to link specific teaching strategies to identified student weaknesses. This study found that artefacts, such as cognitive commentaries that connect assessment, teaching and learning, can help build professional knowledge and expertise, which remain key components of teacher assessment literacy.
Cell culture product quality attribute prediction using convolutional neural networks and Raman spectroscopy
Authors: Khodabandehlou Hamid , Rashedi Mohammad , Wang Tony , Tulsyan Aditya , Schorner Gregg , Garvin Christopher , Undey Cenk
Published: January 2024

Advanced process control in the biopharmaceutical industry often lacks real‐time measurements due to resource constraints. Raman spectroscopy and Partial Least Squares (PLS) models are often used to monitor bioprocess cultures in real‐time. In spite of the ease of training, the accuracy of the PLS model is impacted if it is not used to predict quality attributes for the cell lines it is trained on. To address this issue, a deep convolutional neural network (CNN) is proposed for offline modeling of metabolites using Raman spectroscopy. By utilizing asymmetric least squares smoothing to adjust Raman spectra baselines, a generic training data set is created by amalgamating spectra from various cell lines and operating conditions. This data set, combined with their derivatives, forms a two‐dimensional model input. The CNN model is developed and validated for predicting different quality variables against measurements from various continuous and fed‐batch experimental runs. Validation results confirm that the deep CNN model is an accurate generic model of the process to predict real‐time quality attributes, even in experimental runs not included in the training data. This model is robust and versatile, requiring no recalibration when deployed at different sites to monitor various cell lines and experimental runs.
Identification and validation of cortisol‐related hub biomarkers and the related pathogenesis of biomarkers in Ischemic Stroke
Authors: Wang Jing‐Jing , Xu Fang‐Biao , Hu Sen , Xu Yu‐Ming , Wang Xin‐Zhi
Published: January 2024

Background

Ischemic stroke is a disease in which cerebral blood flow is blocked due to various reasons, leading to ischemia, hypoxia, softening, and even necrosis of brain tissues. The level of cortisol is related to the occurrence and progression of ischemic stroke. However, the mechanism governing their interrelationship is still unclear. The main objective of this study was to identify and understand the molecular mechanism between cortisol and IS.

Methods

The common cortisol‐related biological processes were screened by mutual verification of two data sets and the cortisol‐related hub biomarkers were identified. Modular analysis of protein interaction networks was performed, and the differential pathway analysis of individual genes was conducted by GSVA and GSEA. Drug and transcription factor regulatory networks of hub genes were excavated, and the diagnostic potential of hub genes was analyzed followed by the construction of a diagnostic model.

Results

By screening the two data sets by GSVA, three biological processes with common differences were obtained. After variation analysis, four cortisol‐related hub biomarkers (CYP1B1, CDKN2B, MEN1, and USP8) were selected. Through the modular analysis of the protein‐protein interaction network and double verification of GSVA and GSEA, a series of potential molecular mechanisms of hub genes were discovered followed by a series of drug regulatory networks and transcription factor regulatory networks. The hub biomarkers were found to have a high diagnostic value by ROC; thus, a diagnostic model with high diagnostic efficiency was constructed. The diagnostic value was mutually confirmed in the two data sets.

Conclusion

Four cortisol‐related hub biomarkers are identified in this study, which provides new ideas for the key changes of cortisol during the occurrence of IS.
Combination of different noninvasive brain stimulation treatments for upper limb recovery in stroke patients: A systematic review
Authors: Lerín‐Calvo Alfredo , Rodríguez‐Martínez David , Bernal‐Jiménez Juan‐José , Lerma‐Lara Sergio , Ferrer‐Peña Raúl
Published: January 2024

We report a review of Pubmed (Medline), CENTRAL, Web of Science, and Scopus to test the effectiveness of the combined application of repetitive transcranial magnetic stimulation and transcranial direct current stimulation in the improvement of different functional variables of the upper limb in people with stroke. Two independent reviewers assessed eligibility and evaluated the quality of the studies. Five articles were included in the final review according to the inclusion criteria: Most show statistically significant differences in motor function improvement in favor of the experimental group, but not in activity. Due to the heterogeneity of the observed studies, the results should be interpreted with caution—more high‐quality studies are needed to investigate the effectiveness of these interventions in different stages of stroke patients.
Functional seizures: Are they consistent over time?
Authors: Bahous Elian , Wagner Raz , Herskovitz Moshe
Published: January 2024

Background

Our previous study showed that functional seizures (FS) are consistent in the same patient during a single video EEG monitoring (VEEG). This study aimed to check whether FS remains consistent across VEEG sessions even after several years.

Methods

The study evaluated the consistency of FS across different VEEG sessions using five criteria: FS type, the main anatomical region involved (specifically, the body part most affected during the seizure), other involved anatomical regions, frequency of movements, and duration of FS. Consistency levels were categorized as low (one consistent axis), moderate (two consistent axes), and high (three or more consistent axes).

Results

Fourteen patients were included in the final analysis. The mean time between monitoring was 3.8 ± 2.5 years (0.5–8 year). In 13 of 14 patients, the first and second monitoring events were classified into the same FS category. There was consistency in the main anatomical region involved in 9 out of 12 patients with motor FS. In 9 out of 12 patients with motor FS, the other anatomical regions involved were consistent in both sessions. The mean duration of the FS between sessions was inconsistent in most of the patients. Ten patients were classified with high consistency, one patient with moderate consistency, two patients with low consistency, and in one patient, the events were classified as inconsistent.

Conclusions

Our results show that FS tends to remain consistent in a single patient even after several years, and there is probably no correlation between the degree of consistency and the time between VEEG sessions. These findings have implications for supporting the concept of FS as a consistent phenomenon. Additionally, they may suggest potential avenues for future research to elucidate the origins of FS. Subsequent studies are essential to validate and expand upon these preliminary observations.
Tricaprylin‐based drug crystalline suspension for intramuscular long‐acting delivery of entecavir with alleviated local inflammation
Authors: Jeong Min Young , Ho Myoung Jin , Park Joon Soo , Jeong Hoetaek , Kim Jin Hee , Jang Yong Jin , Shin Doe Myung , Yang In Gyu , Kim Hye Rim , Song Woo Heon , Lee Sangkil , Song Seh Hyon , Choi Yong Seok , Han Young Taek , Kang Myung Joo
Published: January 2024

In order to ensure prolonged pharmacokinetic profile along with local tolerability at the injection site, tricaprylin‐based drug crystalline suspension (TS) was designed and its local distribution, pharmacokinetics, and inflammatory response, were evaluated with conventional aqueous suspension (AS). As model drug particles, entecavir 3‐palmitate (EV‐P), an ester lipidic prodrug for entecavir (EV), was employed. The EV‐P‐loaded TS was prepared by ultra‐sonication method. Prepared TS and conventional AS exhibited comparable morphology (rod or rectangular), median diameter (2.7 and 2.6 μm), crystallinity (melting point of 160–165°C), and in vitro dissolution profile. However, in vivo performances of drug microparticles were markedly different, depending on delivery vehicle. At AS‐injected site, drug aggregates of up to 500 μm were formed upon intramuscular injection, and were surrounded with inflammatory cells and fibroblastic bands. In contrast, no distinct particle aggregation and adjacent granulation was observed at TS‐injected site, with >4 weeks remaining of the oily vehicle in micro‐computed tomographic observation. Surprisingly, TS exhibited markedly alleviated local inflammation compared to AS, endowing markedly lessened necrosis, fibrosis thickness, inflammatory area, and macrophage infiltration. The higher initial systemic exposure was observed with TS compared to AS, but TS provided prolonged delivery of EV for 3 weeks. Therefore, we suggest that the novel TS system can be a promising tool in designing parenteral long‐acting delivery, with improved local tolerability.
Sarcomatoid hepatocellular carcinoma mimics hepatic abscess on contrast‐enhanced ultrasound
Authors: Luo Haibo , Leng Xiaoling , Chen Guiwu , Liu Wenqin , Xie Yanhua
Published: January 2024

Key Clinical Message

Sarcomatoid hepatocellular carcinoma (SHCC) is a rare subtype of hepatocellular carcinoma characterized by abdominal pain or persistent fever with an inflammatory reaction. Here, we report a case of SHCC mimicking hepatic abscess described by not only ultrasonography but also computer tomography. SHCC is a rare subtype of hepatocellular carcinoma characterized by epithelial and mesenchymal tumor features with sarcomatoid morphology. Here, we report a case of SHCC described by ultrasonography and computer tomography as well as confirmed by pathological examination.
Decarbonizing Steam‐Methane Reforming: Enhancing Activity through Joule Heating of a Ni/ZrO2‐Coated FeCrAl Coil
Authors: Ledesma Elmer B. , Idamakanti Meghana , Bollini Praveen , Harold Michael P. , Ratnakar Ram R.
Published: January 2024

This study investigates Joule (resistive) heating as a potential method to electrify the heating process in steam‐methane reforming. The significance and relevance of this research are driven by three factors: (1) increasing global demand for hydrogen as feedstock for chemical manufacturing and refining; (2) expanding hydrogen as a carbon‐free energy carrier; and (3) decarbonizing the production sector of the hydrogen value chain. FeCrAl metal wire coils coated uniformly with Ni/ZrO2 catalyst were used in the Joule heating experiments. The resistive power was supplied in the range 50–90 W by varying voltage across the wire. Results show a notable, sharp increase in methane conversion at a power exceeding 60 W (750 °C estimated wire temperature). The results are compared with those for a conventionally‐heated coated wire as well as Joule‐heated uncoated ZrO2‐only wires to elucidate the roles of Ni and ZrO2 and differences in the heating methods. For a range of power the methane conversion obtained with the Joule‐heated Ni/ZrO2‐coated wire is higher than the conventionally‐heated Ni/ZrO2‐coated wire. The results demonstrate that Joule heating of a catalyst‐coated wire is effective for steam‐methane reforming under the experimental conditions examined in our study. Underlying causes for the interesting conversion features are discussed.
Ensemble Effects on Methanol Oxidation to Formaldehyde on Ferric Molybdate Catalysts
Authors: Bowker Michael , House Matthew , Brookes Catherine , Hellier Pip , Wells Peter
Published: January 2024

The properties of Mo‐doped iron oxide are compared with those of the single oxides of Fe and Mo, and with stoichiometric ferric molybdate for the selective oxidation of methanol. It is found that Mo oxide segregates to the surface of the iron oxide at low loadings, while at higher loadings, but below the stoichiometric ratio, presents layers of ferric molybdate at the surface. The relationship between bulk loading and surface Mo is explored, and it is concluded that the reactivity is dominated by ensemble effects. Simple modelling indicates that four or more Fe cation ensembles are required to combust methanol to CO2, ensembles of two Mo cations are required for selective oxidation to formaldehyde, whereas it seems that isolated single sites of either Fe or Mo produce CO.
The Role of Reactive Natural Deep Eutectic Solvents in Sustainable Biocatalysis
Authors: Buzatu Alina Ramona , Todea Anamaria , Peter Francisc , Boeriu Carmen Gabriela
Published: January 2024

Deep eutectic solvents (DESs) advanced in the past decade as the new generation of green and sustainable extraction and reaction media in biorefineries and in a multitude of chemical and biotechnological processes. Particularly, enzyme catalyzed reactions benefit from the specific properties of DESs, which not only ensure good substrate solubility but also enhance enzyme stability and operational efficiency. Recent studies showed that natural deep eutectic solvents (NADESs) comprising choline chloride or betaine as hydrogen bond acceptor and a large spectrum of natural compounds, such as carbohydrates, polyols carboxylic acids, as hydrogen bond donors, can have multiple functions, acting simultaneously as extraction solvent, reaction medium, source of substrate and source as catalyst. This novel approach for the utilization of multifunctional reactive natural deep eutectic solvents (R‐NADESs) in catalytic conversions opens the way to the development of greener biocatalytic and chemo‐catalytic processes, with simpler downstream processing and minimal discarded wastes, which will speed up their durable implementation in industry. This paper reviews the innovative applications of R‐NADESs in biocatalytic reactions for the synthesis of a large diversity of high value chemicals and materials, including biosurfactants, flavors, biobased building blocks and biobased polymers, with highlight on esterification, transesterification, glycerolysis, polymerization, and redox reactions.
The Catalytic Asymmetric Allylic Alkylation of Acyclic Enolates for the Construction of Quaternary and Tetrasubstituted Stereogenic Centres
Authors: Griffiths Connor M. , Franckevičius Vilius
Published: January 2024

To facilitate the discovery and development of new pharmaceuticals, the demand for novel stereofunctionalised building blocks has never been greater. Whilst molecules bearing quaternary and tetrasubstituted stereogenic centres are ideally suited to explore untapped areas of chemical space, the asymmetric construction ofsterically congested carbon centres remains a longstanding challenge in organic synthesis. The enantioselective assembly of acyclic stereogenic centres is even more demanding due to the need to restrict a much wider range of geometries and conformations of the intermediates involved. In this context, the catalytic asymmetric allylicalkylation (AAA) of acyclic prochiral nucleophiles, namely enolates, has become an indispensable tool to access a range of linearα‐quaternary andα‐tetrasubstituted carbonyl compounds. However, unlike the AAA of cyclic enolates with a fixed enolate geometry, to achieve high levels of stereocontrol in the AAA of acyclic enolates, the stereoselectivity of enolisation must be considered. The aim of this review is to offer acomprehensivediscussion of catalytic AAA reactions of acyclic prochiral enolates and their analogues to generate congested quaternary and tetrasubstituted chiral centres using metal, non‐metal and dual catalysis, with particular focus given to the control of enolate geometry and its impact on the stereochemical outcome of the reaction.