bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Synthesis of Acetobacter pasteurianus Lipid A with a Unique Tetrasaccharide Backbone and Evaluation of Its Immunological Functions
Authors: Yamaura Haruki , Shimoyama Atsushi , Hosomi Koji , Kabayama Kazuya , Kunisawa Jun , Fukase Koichi
Published: April 2024

Lipopolysaccharide (LPS), a cell surface component of Gram‐negative bacteria, activates innate immunity. Its active principle is the terminal glycolipid lipid A. Acetobacter pasteurianus is a Gram‐negative bacterium used in the fermentation of traditional Japanese black rice vinegar (kurozu). In this study, we focused on A. pasteurianus lipid A, which is a potential immunostimulatory component of kurozu. The active principle structure of A. pasteurianus lipid A has not yet been identified. Herein, we first systematically synthesized three types of A. pasteurianus lipid As containing a common and unique tetrasaccharide backbone. We developed an efficient method for constructing the 2‐trehalosamine skeleton utilizing borinic acid‐catalyzed glycosylation to afford 1,1’‐α,α‐glycoside in high yield and stereoselectivity. A common tetrasaccharide intermediate with an orthogonal protecting group pattern was constructed via [2+2] glycosylation. After introducing various fatty acids, all protecting groups were removed to achieve the first chemical synthesis of three distinct types of A. pasteurianus lipid As. After evaluating their immunological function using both human and murine cell lines, we identified the active principles of A. pasteurianus LPS. We also found the unique anomeric structure of A. pasteurianus lipid A contributes to its high chemical stability.
One‐Step Butadiene Purification in a Sulfonate‐Functionalized Metal–Organic Framework through Synergistic Separation Mechanism
Authors: Cui Jiyu , Qiu Zhensong , Yang Zhenglu , Jin Anye , Cui Xili , Yang Lifeng , Xing Huabin
Published: April 2024

Porous materials that could recognize specific molecules from complex mixtures are of great potential in improving the current energy‐intensive multistep separation processes. However, due to the highly similar structures and properties of the mixtures, the design of desired porous materials remains challenging. Herein, a sulfonate‐functionalized metal–organic framework ZU‐609 with suitable pore size and pore chemistry is designed for 1,3‐butadiene (C4H6) purification from complex C4 mixtures. The sulfonate anions decorated in the channel achieve selective recognition of C4H6 from other C4 olefins with subtle polarity differences through C−H⋅⋅⋅O−S interactions, affording recorded C4H6/trans‐2‐C4H8 selectivity (4.4). Meanwhile, the shrunken mouth of the channel with a suitable pore size (4.6 Å) exhibits exclusion effect to the larger molecules cis‐2‐C4H8, iso‐C4H8, n‐C4H10 and iso‐C4H10. Benefiting from the moderate C4 olefins binding affinity exhibited by sulfonate anions, the adsorbed C4H6 could be easily regenerated near ambient conditions. Polymer‐grade 1,3‐butadiene (99.5 %) is firstly obtained from 7‐component C4 mixtures via one adsorption‐desorption cycle. The work demonstrates the great potential of synergistic recognition of size‐sieving and thermodynamically equilibrium in dealing with complex mixtures.
Temperature‐Controlled Selective Formation of Silver Nanoclusters and Their Transformation to the Same Product
Authors: Wang Zhi , Wang Yuchen , Xu Tian‐Yang , Li Li , Aikens Christine M. , Gao Zhi‐Yong , Azam Mohammad , Tung Chen‐Ho , Sun Di
Published: April 2024

Herein, two atomically precise silver nanoclusters, Ag54 and Ag33, directed by inner anion templates (CrO42− and/or Cl−), are initially isolated as a mixed phase from identical reactants across a wide temperature range (20–80 °C). Interestingly, fine‐tuning the reaction temperature can realize pure phase synthesis of the two nanoclusters; that is, a metastable Ag54 is kinetically formed at a low temperature (20 °C), whereas such a system is steered towards a thermodynamically stable Ag33 at a relatively high temperature (80 °C). Electrospray ionization mass spectrometry illustrates that the stability of Ag33 is superior to that of Ag54, which is further supported by density functional theory calculations. Importantly, the difference in structural stability can influence the pathway of 1,4‐bis(pyrid‐4‐yl)benzene induced transformation reaction starting from Ag54 and Ag33. The former undergoes a dramatic breakage‐reorganization process to form an Ag31 dimer (Ag31), while the same product can be also achieved from the latter following a noninvasive ligand exchange process. Both the Ag54 and Ag33 have the potential for further remote laser ignition applications. This work not only demonstrates how temperature controls the isolation of a specific phase, but also sheds light on the structural transformation pathway of nanoclusters with different stability.
Covalent Organic Framework Interlayer Spacings as Perfectly Selective Artificial Proton Channels
Authors: Li Qi , Gao Hongfei , Zhao Yongye , Zhou Bo , Yu Lei , Huang Qingsong , Jiang Lei , Gao Jun
Published: April 2024

Biological proton channels have perfect selectivity in aqueous environment against almost all ions and molecules, a property that differs itself from other biological channels and a feature that remains challenging to realize for bulk artificial materials. The biological perfect selectivity originates from the fact that the channel has almost no free space for ion or water transport but generates a hydrogen bonded wire in the presence of protons to allow the proton hopping. Inspired by this, we used the interlayer spacings of covalent organic framework materials consisting of hydrophilic functional groups as perfectly selective artificial proton channels. The interlayer spacings are so narrow that no atoms or molecules can diffuse through. However, protons exhibit a diffusivity in the same order of magnitude as that in bulk water. Density functional theory calculations show that water molecules and the COF material form hydrogen bonded wires, allowing the proton hopping. We further demonstrate that the proton transport rate can be tuned by adjusting the acidity of the functional groups.
Tandem Catalysts Enabling Efficient C−N Coupling toward the Electrosynthesis of Urea
Authors: Gao Yuhang , Wang Jingnan , Sun Menglong , Jing Yuan , Chen Lili , Liang Zhiqin , Yang Yijun , Zhang Chuang , Yao Jiannian , Wang Xi
Published: April 2024

The development of a methodology for synthesizing value‐added urea (CO(NH2)2) via a renewable electricity‐driven C−N coupling reaction under mild conditions is highly anticipated. However, the complex catalytic active sites that act on the carbon and nitrogen species make the reaction mechanism unclear, resulting in a low efficiency of C−N coupling from the co‐reduction of carbon dioxide (CO2) and nitrate (NO3−). Herein, we propose a novel tandem catalyst of Mo‐PCN‐222(Co), in which the Mo sites serve to facilitate nitrate reduction to the *NH2 intermediate, while the Co sites enhance CO2 reduction to carbonic oxide (CO), thus synergistically promoting C−N coupling. The synthesized Mo‐PCN‐222(Co) catalyst exhibited a noteworthy urea yield rate of 844.11 mg h−1 g−1, alongside a corresponding Faradaic efficiency of 33.90 % at −0.4 V vs. reversible hydrogen electrode (RHE). By combining in situ spectroscopic techniques with density functional theory calculations, we demonstrate that efficient C−N coupling is attributed to a tandem system in which the *NH2 and *CO intermediates produced by the Mo and Co active sites of Mo‐PCN‐222(Co) stabilize the formation of the *CONH2 intermediate. This study provides an effective avenue for the design and synthesis of tandem catalysts for electrocatalytic urea synthesis.
Semi‐aromatic polyamide containing ether bond/hydroxyapatite composites: Preparation, structure and cytocompatibility
Authors: Chen Chaobi , Lyu Defu , Xi Wenjing , Chen Lichao , Cai Shijie , Yan Yonggang , Li Xiaodan , Ren Haohao , Xing Rong
Published: April 2024

In this work, semi‐aromatic polyamide containing ether bond (PAE10T) was synthesized through nucleophilic substitution reaction using 1, 10‐N, N′‐bis(4‐fuorobenzamide) decane (BFBD) and hydroquinone (HQ) as the raw materials. And then the composites hydroxyapatite/semi‐aromatic polyamide (40%HA‐PAE10T and 60%HA‐PAE10T) were prepared by chemical precipitation method. Mechanical, SEM, FT‐IR, XRD, DSC, TGA and bioactivity tests were performed to characterize the structure, morphology, thermal and mechanical properties of PAE10T and its composites. Mechanical tests revealed that the difference of HA in weight played an important role in mechanical performance of the composites. Furthermore, in comparison with PAE10T, the 60%HA‐PAE10T showed the highest enhancement in compressive strength (133 MPa) at 75.9%, and the 40%HA‐PAE10T given expression to the best increase in bending strengths (97 MPa) at about 18.4%. The 40%HA‐PAE10T and 60% HA‐PAE10T exhibited the mechanical performances closed to the cortical bone of human. After 28 days of dip in the phosphate buffer saline (PBS), PAE10T, and its composites showed satisfactory stability. The cell culture results showed all composites gad good cytocompatibility, cells attached on the materials well with excellent morphology. All the experimental results showed that the composites were expected to have a good application in the field of compact bone repair.
Effects of blending poly (polyol sebacate) and poly (polyol adipate) bioelastomers for soft tissue engineering in biomedical applications
Authors: Norouznezhad Afshin , Mir Mohamad Sadeghi Gity
Published: April 2024

In this article, the synthesis of four novel bioelastomers known as poly (xylitol sebacate) (PXS), poly (xylitol adipate) (PXA), poly (sorbitol sebacate) (PSS), and poly (sorbitol adipate) (PSA) was carried out through bulk polymerization, followed by their blending using the solution method. Six blends were prepared namely PXS25/PSS75, PXS50/PSS50, PXS75/PSS25, PXS50/PXA50, PSA50/PXA50, and PSS50/PSA50. After blending, a thermal curing process was applied to the samples. The intrinsic viscosity, density, Tg, hydrophilicity, degradation, wound healing, and mechanical properties of polymers and blends were measured to investigate the effects of blending. Analyzing hardness, modulus, stress at breakpoint, degradation, and hydrophilicity data showed that the mechanical properties of bioelastomers are adjustable by blending for tissue engineering. Furthermore, the scratch assay proved the biocompatibility of pure polymers and indicated that blending does not have a negative impact on this matter.
From postconsumer cotton towels to new cotton textile fibers
Authors: Schlapp‐Hackl Inge , Rissanen Marja , Ojha Krishna , Sawada Daisuke , Gorniak Kasia , Onkinen Elina , Niinimäki Kirsi , Sixta Herbert
Published: April 2024

The chemical recycling of cotton towels via the Ioncell® technique is demonstrated. Cotton is the most common natural fiber. The season's value jumped 31% to 54.3 billion US$ in 2020/2021, and annually the average value in quota‐free periods accounts to 46.3 billion US$. Consequently, enormous amounts of cotton wastes are emerging. Especially, European countries are forced by the new legislation of the union to develop new recycling strategies. Due to uncountable cotton applications, various types of garments exist, which require different recycling strategies. The recycling of an additional cotton waste side stream of Lindström Oy white pre and dyed and white postconsumer cotton roll towels was pursued. The mechanical properties of the fibers and yarns have been evaluated. Thereby, the following elongations and tenacities of conditioned fibers produced at DR11 have been achieved: 10.4%/59.5 cN/tex for preconsumer and 10.6%/60.4 cN/tex for postconsumer white cotton, 10.4%/60.0 cN/tex for postconsumer blue cotton. The achieved elongations at break are close to values reported in literature (7%–14%), however, the tenacities exceed reported values (40–58 cN/tex). Highly oriented fibers of high quality have been produced and with regards to the mechanical properties, a technique to perform fiber‐to‐fiber upcycling is illustrated.
Enhancing the piezoelectric performance of composite PVDF flexible films through optimizing β phase content, investigating additive effects, step‐wise polarization, and thermal pressing time for energy harvesting applications
Authors: Oflaz Kamil , Özaytekin İlkay , Sadasivuni Kishor Kumar
Published: April 2024

Polyvinylidene fluoride (PVDF), known for its piezoelectric versatility, emerges as a key contender for advancing efficient and sustainable energy harvesting in nanogenerators. This study explores the potential enhancement of piezoelectric properties in flexible PVDF polymers, employing a comprehensive approach through the solution casting method. The investigation integrates diverse additives, thermal treatments, and polarization methods to optimize performance, focusing on the impact of the β phase transition on electrical voltage generation. Utilizing the Taguchi experimental design, the study identifies optimal conditions for the composite PVDF film (OPT‐PVDF) through FT‐IR, XRD, and DSC analyses, with output voltage measurements confirming superior performance compared to pure PVDF (P‐PVDF). Specifically, BN‐doped PVDF films, with an 80% β phase content, achieve an impressive 6.48 V output voltage. This research underscores PVDF's potential for energy harvesting, emphasizing the pivotal role of optimizing β phase content, additive strategies, and the effects of polarization and thermal treatments. The study further evaluates the effect and necessity of subsequent thermal treatment and step‐wise polarization effects on the composite PVDF film material. The findings indicate that BN‐doped composite PVDF films, produced under optimal conditions, exhibit advanced piezoelectric properties.
Multiscale mechanics of polydimethylsiloxane: A comparison of meso‐ and micro‐cyclic deformation behavior
Authors: Lou Lihua , Bacca Nicole , Ma Marshall S. , Nautiyal Pranjal , Bifano Thomas G. , Agarwal Arvind
Published: April 2024

Despite plenty of static and dynamic mechanical measurements and modeling for bulk polydimethylsiloxane (PDMS) specimens, a notable gap exists in comprehensively understanding the dynamic mechanics under large cycle, low strain conditions, especially for microscale samples. This study integrates tensile testing and nanoindentation techniques to compare dynamic mechanical response for bulk PDMS samples and μ‐pillars. The results from cyclic tensile testing, which involved up to 10,000 cycles at a strain range of 10%–20%, indicate a stabilization of energy dissipation rate after the initial 25 cycles. This attributes to stress relaxation and strain hardening, validating by rapid dual‐phase exponential decay in maximum stress, coupled with an incremental increase in elastic modulus. In comparison to tensile testing, μ‐pillars exhibited a 0.82% reduction in stiffness, stabilizing ~600th cycle. Concurrently, there was an approximately twofold increase in approaching distance during the initial 120 cycles, and an approximately fourfold increase in dissipated energy over the first 80 cycles, before reaching a plateau. This lagging hysteresis effect attributes to the distribution of the resultant force, including top tension, bottom compression, and base tilt. Overall, this study illuminates temporal mechanical deformations in PDMS under two application scenarios, enhancing our understanding of PDMS mechanical behavior.
Cellulose nanowhiskers‐reinforced polymer nanofibers for photoresponsive authentication
Authors: Gouda Mohamed , Khalaf Mai M. , Abou Taleb Manal F. , Abd El‐Lateef Hany M.
Published: April 2024

The objective of the current study is to develop novel photochromic polyurethane (PUR) nanofibrous films supported with cellulose nanowhiskers (CNW) and immobilized with nanoparticles of alkaline‐earth doped aluminate (NAEA) using the highly efficient and low‐cost solution blowing spinning (SBS) technique. CNW revealed a crystal diameter of 4–8 nm, and a crystal length of 55–105 nm. The solution blown spun nanofibers exhibited diameters of 250–450 nm. In order to prepare a transparent film, CNW and NAEA must be dispersed efficiently in the PUR composite. When supported with CNW, the efficiency of PUR nanofibrous films was strengthened. Cellulose paper sheets were coated with the colorless NAEA/CNW@PUR films to emit a green light at 518 nm upon excitation at 365 nm as proved by photoluminescence spectra. The prepared nanofibrous films exhibited efficient optical photochromic characteristics for potential security encoding applications. The nanofibers‐coated papers showed high photochromic reversibility without fatigue. The current approach can be reported as an efficient technology for authentication of commercial products.
Optimizing the preparation parameters of eco‐friendly flexible polyurethane foams derived from a corn‐based bio‐polyol
Authors: Park Jun Hak , Jo Kyung Il , Kim Il Jin , Kwon Taehoon , Yu Seunggun , Ko Jae Wang , Lee Jin Hong
Published: April 2024

Corn‐based bio‐polyol is employed as an alternative for petroleum‐based polyol to prepare an eco‐friendly polyurethane (PU) foam via a one‐shot method. By varying ratio of gelling catalyst, blowing catalyst, and surfactant during the preparation process, the compression performance, cell morphology, and thermal stability of the PU foam are analyzed. The results obtained indicate that an increase in surfactant content yielded improved foam stability, whereas increased amounts of blowing and gelling catalysts resulted in enhanced compression performance. An optimized foaming process is determined with an NCO/OH ratio of 1.2, 0.2 parts per hundred polyols (pphp) of gelling catalyst, 0.1 pphp of blowing catalyst, and 0.1 pphp of surfactant. Under these specific conditions, the PU foam exhibits a uniform cell structure, exceptional compression performance, and good thermal stability, comparable to those of a reference foam derived from petroleum‐based polyol.
Improving performance of aerosol jet printing using machine learning‐driven optimization
Authors: Pandey Prashantkumar , Ziesche Steffen , Meghanathi Gauranggiri
Published: April 2024

Aerosol jet printing is a promising technology for printing functional materials on a variety of substrates with high precision and resolution. This technology has the potential to revolutionize the manufacturing industry by providing a low‐cost, high‐resolution printing technique that can be used to produce additively printed electronics, sensors, and energy devices. However, the optimization of this process has traditionally relied on time‐consuming trial‐and‐error methods, hampering its efficiency and scalability. Machine learning (ML) models have the potential to overcome these challenges and improve the quality, speed, and efficiency of the printing process. In this paper, we propose an approach that leverages ML algorithms to streamline and enhance the aerosol jet printing optimization process. Our methodology involves data collection through systematic experimentation with various parameter settings. This data set serves as the foundation for training different ML model capable of predicting printed line characteristics and optimal printing process parameter. We validate our approach by performing experiments on different inks, and we compare the results of our ML‐based optimization approach to those obtained using traditional trial‐and‐error methods. The results demonstrate that our approach offers significantly higher accuracy and efficiency. To enhance our approach's accessibility and ease of use, we incorporate AutoML techniques which automates the process of selecting the most suitable ML algorithms and hyperparameters, reducing the burden of manual configuration. Furthermore, we introduce a user‐friendly web‐based interface that facilitates the entire ML pipeline, from data preprocessing to prediction and batch processing. This interface empowers users to efficiently manage and manipulate their data, select appropriate ML algorithms, and execute predictions, ultimately improving accuracy and model performance.
A machine learning approach to study plant functional trait divergence
Authors: Majumder Sambadi , Mason Chase M.
Published: April 2024

Premise

Plant functional traits are often used to describe the spectra of ecological strategies used by different species. Here, we demonstrate a machine learning approach for identifying the traits that contribute most to interspecific phenotypic divergence in a multivariate trait space.

Methods

Descriptive and predictive machine learning approaches were applied to trait data for the genus Helianthus, including random forest and gradient boosting machine classifiers and recursive feature elimination. These approaches were applied at the genus level as well as within each of the three major clades within the genus to examine the variability in the major axes of trait divergence in three independent species radiations.

Results

Machine learning models were able to predict species identity from functional traits with high accuracy, and differences in functional trait importance were observed between the genus and clade levels indicating different axes of phenotypic divergence.

Conclusions

Applying machine learning approaches to identify divergent traits can provide insights into the predictability or repeatability of evolution through the comparison of parallel diversifications of clades within a genus. These approaches can be implemented in a range of contexts across basic and applied plant science from interspecific divergence to intraspecific variation across time, space, and environmental conditions.
Persistence of changed attitudes among students in an integrated anatomy curriculum
Authors: Rosenberg Martina J. , Hartley Rebecca S.
Published: April 2024

Many medical schools in the United States have integrated anatomy into an organ‐based preclinical curriculum with some schools using anatomy as the cornerstone of their reorganization efforts. Curricular change could affect one or more of the three domains of learning, with the cognitive domain often scrutinized exclusively. A previous study reported the impact of anatomy integration on the affective domain, specifically, student attitudes toward learning anatomy. This mixed methods follow‐up study asked if the observed attitudinal changes and lack of effect on student knowledge and confidence persisted using knowledge and confidence surveys, focus groups, internal and national surveys, and United States Medical Licensing Examination® performance metrics. Results evidenced the persistence of specific attitudinal differences between cohorts with blocked versus integrated anatomy with no apparent short‐ or long‐term differences in anatomy learning or confidence in this learning. Altered attitudes included lower value placed on working in teams and reflective practices, and less recognition of anatomy's contribution (or less contribution of anatomy learning) to professional identity formation. These attitudinal changes could result in a weaker foundation for building collaborative skills throughout the medical curriculum. A decreased sense of student engagement also followed curricular change, as assessed by data from the American Association of Medical Colleges Year 2 Questionnaire. Overall, results emphasized the necessity of anticipating, monitoring, and if necessary, addressing changes in the affective domain when undertaking curricular change.
To persist or not? Examining the relations between parental education, self‐regulation, school engagement and persistence in post‐compulsory education
Authors: Katsantonis Ioannis , Gibbons Ryan Alberto , Symonds Jennifer E. , Costello Niall
Published: April 2024

There are few longitudinal studies of adolescent students’ choice to persist in post‐compulsory education. Hence, the present study introduces a longitudinal model that describes the interplay between sociological and psychological explanations of adolescents’ choice to persist in post‐compulsory education in the UK. Data on parental education, early childhood self‐regulation (age 5), sustained school engagement (ages 7, 11, 14) and persistence in education after the end of compulsory schooling (age 17) were utilised. The sample comprised 8333 (51.1% females, 89.5% white) children from the Millennium Cohort Study. Statistical analyses included state–trait modelling, longitudinal mediation and multigroup moderation. A trait–state–occasion model was run to disentangle the trait from state variance in school engagement. Afterwards, two hypotheses were formulated, namely the ‘instilment’ and the ‘differential’. The ‘instilment’ hypothesis involved a longitudinal predictive model, whereby parental education predicted early childhood self‐regulation which, in turn, predicted sustained school engagement which predicted students’ choice to persist. The ‘differential’ hypothesis examined whether higher vs. lower parental education changed the nature of the predictive relations between self‐regulation, sustained school engagement and persistence. The results were in favour of an ‘instilment’ hypothesis, whereby higher parental education was translated to higher levels of early self‐regulation which predicted higher sustained engagement, which, in turn, predicted greater probability of persisting in post‐compulsory education. The findings suggest a pathway from early childhood experiences to educational outcomes via the development of a trait of engaging with school.
Beta spending function based on conditional power in group sequential design
Authors: Ni Senmiao , Zhong Zihang , Jiang Zhiwei , Zhao Yang , Wu Jingwei , Yu Hao , Bai Jianling
Published: April 2024

Conditional power (CP) serves as a widely utilized approach for futility monitoring in group sequential designs. However, adopting the CP methods may lead to inadequate control of the type II error rate at the desired level. In this study, we introduce a flexible beta spending function tailored to regulate the type II error rate while employing CP based on a predetermined standardized effect size for futility monitoring (a so‐called CP‐beta spending function). This function delineates the expenditure of type II error rate across the entirety of the trial. Unlike other existing beta spending functions, the CP‐beta spending function seamlessly incorporates beta spending concept into the CP framework, facilitating precise stagewise control of the type II error rate during futility monitoring. In addition, the stopping boundaries derived from the CP‐beta spending function can be calculated via integration akin to other traditional beta spending function methods. Furthermore, the proposed CP‐beta spending function accommodates various thresholds on the CP‐scale at different stages of the trial, ensuring its adaptability across different information time scenarios. These attributes render the CP‐beta spending function competitive among other forms of beta spending functions, making it applicable to any trials in group sequential designs with straightforward implementation. Both simulation study and example from an acute ischemic stroke trial demonstrate that the proposed method accurately captures expected power, even when the initially determined sample size does not consider futility stopping, and exhibits a good performance in maintaining overall type I error rates for evident futility.
Proteomic analysis reveals that the co‐ordination of cytosolic and mitochondrial pathways is beneficial for sabinene biosynthesis in engineered Saccharomyces cerevisiae
Authors: Hou Rui , Shan Mengying , Liu Xinxin , Yao Mingdong , Yang Kaiguang , Wang Ying , Sui Zhigang , Liang Zhen , Zhang Yukui , Zhang Lihua
Published: April 2024

Reconstruction and optimization of biosynthetic pathways can help to overproduce target chemicals in microbial cell factories based on genetic engineering. However, the perturbation of biosynthetic pathways on cellular metabolism is not well investigated and profiling the engineered microbes remains challenging. The rapid development of omics tools has the potential to characterize the engineered microbial cell factory. Here, we performed label‐free quantitative proteomic analysis and metabolomic analysis of engineered sabinene overproducing Saccharomyces cerevisiae strains. Combined metabolic analysis andproteomic analysis of targeted mevalonate (MVA) pathway showed that co‐ordination of cytosolic and mitochondrial pathways had balanced metabolism, and genome integration of biosynthetic genes had higher sabinene production with less MVA enzymes. Furthermore, comparative proteomic analysis showed that compartmentalized mitochondria pathway had perturbation on central cellular metabolism. This study provided an omics analysis example for characterizing engineered cell factory, which can guide future regulation of the cellular metabolism and maintaining optimal protein expression levels for the synthesis of target products.
Transcriptomic analysis provides an insight into the function of CmGH9B3, a key gene of β‐1, 4‐glucanase, during the graft union healing of oriental melon scion grafted onto squash rootstock
Authors: Zhu Yulei , Hu Shengwei , Min Jiahuan , Zhao Yingtong , Yu Hanqi , Irfan Muhammad , Xu Chuanqiang
Published: April 2024

The melon (Cucumis melo L.) is a globally cherished and economically significant crop. The grafting technique has been widely used in the vegetative propagation of melon to promote environmental tolerance and disease resistance. However, mechanisms governing graft healing and potential incompatibilities in melons following the grafting process remain unknown. To uncover the molecular mechanism of healing of grafted melon seedlings, melon wild type (Control) and TRV‐CmGH9B3 lines were obtained and grafted onto the squash rootstocks (C. moschata). Anatomical differences indicated that the healing process of the TRV‐CmGH9B3 plants was slower than that of the control. A total of 335 significantly differentially expressed genes (DEGs) were detected between two transcriptomes. Most of these DEGs were down‐regulated in TRV‐CmGH9B3 grafted seedlings. GO and KEGG analysis showed that many metabolic, physiological, and hormonal responses were involved in graft healing, including metabolic processes, plant hormone signaling, plant MAPK pathway, and sucrose starch pathway. During the healing process of TRV‐CmGH9B3 grafted seedlings, gene synthesis related to hormone signal transduction (auxin, cytokinin, gibberellin, brassinolide) was delayed. At the same time, it was found that most of the DEGs related to the sucrose pathway were down‐regulated in TRV‐CmGH9B3 grafted seedlings. The results showed that sugar was also involved in the healing process of melon grafted onto squash. These results deepened our understanding of the molecular mechanism of GH9B3, a key gene of β‐1, 4‐glucanase. It also provided a reference for elucidating the gene mechanism and function analysis of CmGH9B3 in the process of graft union healing.
Atomically precise metal nanoclusters for energy conversion
Authors: Seong Hoeun , Lee Dongil
Published: April 2024

Atomically precise metal nanoclusters (NCs) have emerged as a new frontier in electrocatalysis, enabling the study of electrocatalytic reactions on well‐defined stable surfaces and rational electrocatalyst design based on atomic‐level tailoring. In this review, we focus on the recent applications of these NCs to energy conversion reactions, including those involved in water splitting (hydrogen and oxygen evolution reactions), fuel cell operation (oxygen reduction and hydrogen oxidation reactions), and electrochemical CO2 reduction. Emblematic examples are used to highlight the roles of different NC parts, for example, core metal and surrounding ligands, and the significance of the electrode substrate. Finally, we discuss the perspectives of the future development and implementation of NC‐based energy conversion systems.
A double‐edged sword: The complex interplay between engineered nanoparticles and platelets
Authors: Asaad Yathreb , Nemcovsky‐Amar Danielle , Sznitman Josué , Mangin Pierre H. , Korin Netanel
Published: April 2024

Nanoparticles (NP) play a crucial role in nanomedicine, serving as carriers for localized therapeutics to allow for precise drug delivery to specific disease sites and conditions. When injected systemically, NP can directly interact with various blood cell types, most critically with circulating platelets. Hence, the potential activation/inhibition of platelets following NP exposure must be evaluated a priori due to possible debilitating outcomes. In recent years, various studies have helped resolve the physicochemical parameters that influence platelet‐NP interactions, and either emphasize nanoparticles' therapeutic role such as to augment hemostasis or to inhibit thrombus formation, or conversely map their potential undesired side effects upon injection. In the present review, we discuss some of the main effects of several key NP types including polymeric, ceramic, silica, dendrimers and metallic NPs on platelets, with a focus on the physicochemical parameters that can dictate these effects and modulate the therapeutic potential of the NP. Despite the scientific and clinical significance of understanding Platelet‐NP interactions, there is a significant knowledge gap in the field and a critical need for further investigation. Moreover, improved guidelines and research methodologies need to be developed and implemented. Our outlook includes the use of biomimetic in vitro models to investigate these complex interactions under both healthy physiological and disease conditions.
Variation in the origin of the plantar aponeurosis and its relationship to the origin of the abductor hallucis muscle
Authors: Mizuno Daisuke , Otsuka Shun , Shan Xiyao , Umemoto Kanae , Naito Munekazu
Published: April 2024

The plantar aponeurosis comprises medial, central, and lateral bands, which arise from the calcaneal tuberosity. Descriptions of the origin of the abductor hallucis vary among different textbooks. The central band and abductor hallucis muscles are related to the windlass mechanism. Given the uncertainties regarding the details of the origins of the central band and the abductor hallucis muscle, we examined those origins in 100 feet of 50 cadavers (25 males and 25 females) by dissection. There were three central band patterns, depending on the attachment sites of the origins of the central and lateral bands: Pattern Ia, the central band covers the lateral band completely; Pattern Ib, the central band covers part of the lateral band; Pattern II, the lateral band covers part of the central band. The origin of the abductor hallucis muscle was confirmed. It showed two types of variation: attachment type, originating from the central band; non‐attachment type, not originating from the central band. Central band Patterns Ia, Ib, and II were found in 23 feet (17 males, 6 females), 24 feet (25 males, 28 females), and 24 feet (eight males, 16 females), respectively. Pattern Ia predominated in males and Pattern II in females. The attachment and non‐attachment types of abductor hallucis muscle were observed in 28 feet (28%) and 72 feet (72%), respectively. The attachment type with Patterns Ia, Ib, and II was shown in 17 feet, 10 feet, and one foot, respectively. Thus, we revealed variation and sex differences in the central band, which could affect foot morphology and the efficacy of the windlass mechanism.
RSPO3 induced by Helicobacter pylori extracts promotes gastric cancer stem cell properties through the GNG7/β‐catenin signaling pathway
Authors: Rao Xiwu , Zhang Zhipeng , Pu Yunzhou , Han Gang , Gong Hangjun , Hu Hao , Ji Qing , Liu Ningning
Published: April 2024

Background

Helicobacter pylori (H. pylori) accounts for the majority of gastric cancer (GC) cases globally. The present study found that H. pylori promoted GC stem cell (CSC)‐like properties, therefore, the regulatory mechanism of how H. pylori promotes GC stemness was explored.

Methods

Spheroid‐formation experiments were performed to explore the self‐renewal capacity of GC cells. The expression of R‐spondin 3 (RSPO3), Nanog homeobox, organic cation/carnitine transporter‐4 (OCT‐4), SRY‐box transcription factor 2 (SOX‐2), CD44, Akt, glycogen synthase kinase‐3β (GSK‐3β), p‐Akt, p‐GSK‐3β, β‐catenin, and G protein subunit gamma 7 (GNG7) were detected by RT‐qPCR, western blotting, immunohistochemistry (IHC), and immunofluorescence. Co‐immunoprecipitation (CoIP) and liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) were performed to identify proteins interacting with RSPO3. Lentivirus‐based RNA interference constructed short hairpin (sh)‐RSPO3 GC cells. Small interfering RNA transfection was performed to inhibit GNG7. The in vivo mechanism was verified using a tumor peritoneal seeding model in nude mice.

Results

H. pylori extracts promoted a CSC‐like phenotype in GC cells and elevated the expression of RSPO3. RSPO3 knockdown significantly reduced the CSC‐like properties induced by H. pylori. Previous studies have demonstrated that RSPO3 potentiates the Wnt/β‐catenin signaling pathway, but the inhibitor of Wnt cannot diminish the RSPO3‐induced activation of β‐catenin. CoIP and LC–MS/MS revealed that GNG7 is one of the transmembrane proteins interacting with RSPO3, and it was confirmed that RSPO3 directly interacted with GNG7. Recombinant RSPO3 protein increased the phosphorylation level of Akt and GSK‐3β, and the expression of β‐catenin in GC cells, but this regulatory effect of RSPO3 could be blocked by GNG7 knockdown. Of note, GNG7 suppression could diminish the promoting effect of RSPO3 to CSC‐like properties. In addition, RSPO3 suppression inhibited MKN45 tumor peritoneal seeding in vivo. IHC staining also showed that RSPO3, CD44, OCT‐4, and SOX‐2 were elevated in H. pylori GC tissues.

Conclusion

RSPO3 enhanced the stemness of H. pylori extracts‐infected GC cells through the GNG7/β‐catenin signaling pathway.
Carane‐3,4‐diol Derivatives as Potential Water‐Based Herbicides
Authors: Huang Yanqun , Zhu Maomao , Lan Hongyun , Huang Daozhan , Lan Mengna , Huang Yanning
Published: April 2024

Twelve novel carane‐3,4‐diol derivatives were designed, synthesized, and evaluated for their herbicidal activities against Lolium multiflorum Lam. and Brassica campestris for the first time. The relationships between the chemical structural factors, including types, the number or the carbon chain length of functional groups, associated with the lipophilicity and the herbicidal activity of the tested compounds were also discussed. The results showed that most of newly synthesized compounds had a dose‐dependent, herbicidal activity against the root and shoot growths of Lolium multiflorum Lam. and Brassica campestris. Compared to carane‐3,4‐diol, most of the target derivatives possessed improved lipophilicity and certain solubilities in representative solvents with different polarities. Particularly, ester derivatives 3a–3b and 3e can be dissolved or dispersed in water, but also displayed higher herbicidal activity against Lolium multiflorum Lam. and Brassica campestris than other ester derivatives. The 50 % inhibitory concentration (IC50) value of compound 3e against shoot growth of Brassica campestris (0.485 mmol/L) was superior to that of commercial herbicide glyphosate (1.14 mmol/L), indicating that the potential application as a water‐based herbicide for Brassica campestris control.
Identifying Anti‐NSCLC Bioactive Compounds in Scutellaria via 2D NMR‐Based Metabolomic Analysis of Pharmacologically Classified Crude Extracts
Authors: Chen Jialuo , Li Yanping , Gu Xiu , Wu Tianren , Du Huan , Bai Caihong , Yang Jiahui , Hu Kaifeng
Published: April 2024

We presented a strategy utilizing 2D NMR‐based metabolomic analysis of crude extracts, categorized by different pharmacological activities, to rapidly identify the primary bioactive components of TCM. It was applied to identify the potential bioactive components from Scutellaria crude extracts that exhibit anti‐non‐small cell lung cancer (anti‐NSCLC) activity. Four Scutellaria species were chosen as the study subjects because of their close phylogenetic relationship, but their crude extracts exhibit significantly different anti‐NSCLC activity. Cell proliferation assay was used to assess the anti‐NSCLC activity of four species of Scutellaria. 1H−13C HSQC spectra were acquired for the chemical profiling of these crude extracts. Based on the pharmacological classification (PCA, OPLS‐DA and univariate hypothesis test) were performed to identify the bioactive constituents in Scutellaria associated with the anti‐NSCLC activity. As a result, three compounds, baicalein, wogonin and scutellarin were identified as bioactive compounds. The anti‐NSCLC activity of the three potential active compounds were further confirmed via cell proliferation assay. The mechanism of the anti‐NSCLC activity by these active constituents was further explored via flow cytometry and western blot analyses. This study demonstrated 2D NMR‐based metabolomic analysis of pharmacologically classified crude extracts to be an efficient approach to the identification of active components of herbal medicine.
Strategies to Design Chemocatalytic Racemization of Tertiary Alcohols: State of the Art & Utilization for Dynamic Kinetic Resolution
Authors: Gröger Harald , Horino Satoshi , Kanomata Kyohei , Akai Shuji
Published: April 2024

The synthesis of enantiomerically pure tertiary alcohols is an important issue in organic synthesis of a range of pharmaceuticals including molecules such as the anti‐HIV drug Efavirenz. A conceptually elegant approach to such enantiomers is the dynamic kinetic resolution of racemic tertiary alcohols, which, however, requires efficient racemization strategies. The racemization of tertiary alcohols is particularly challenging due to various side reactions that can occur because of their high tendency for elimination reactions. In the last few years, several complementary catalytic concepts for racemization of tertiary alcohols have been developed, characterized by efficient racemization and suppression of unwanted side‐reactions. Besides resins bearing sulfonic acid moieties and a combination of boronic acid and oxalic acid as heterogeneous and homogeneous Brønsted‐acids, respectively, immobilized oxovanadium and piperidine turned out to be useful catalysts. The latter two catalysts, which have already been applied to different types of substrates, also have proven good compatibility with lipase, thus leading to the first two examples of chemoenzymatic dynamic kinetic resolution of tertiary alcohols. In this review, the difficulties in racemizing tertiary alcohols are specifically described, and the recently developed complementary concepts to overcome these hurdles are summarized.
Application of an NMR/Crystallography Fragment Screening Platform for the Assessment and Rapid Discovery of New HIV‐CA Binding Fragments
Authors: Lang Stuart , Fletcher Daniel A. , Petit Alain‐Pierre , Luise Nicola , Fyfe Paul , Zuccotto Fabio , Porter David , Hope Anthony , Bellany Fiona , Kerr Catrina , Mackenzie Claire J. , Wyatt Paul G. , Gray David W.
Published: April 2024

Identification and assessment of novel targets is essential to combat drug resistance in the treatment of HIV/AIDS. HIV Capsid (HIV‐CA), the protein playing a major role in both the early and late stages of the viral life cycle, has emerged as an important target. We have applied an NMR fragment screening platform and identified molecules that bind to the N‐terminal domain (NTD) of HIV‐CA at a site close to the interface with the C‐terminal domain (CTD). Using X‐ray crystallography, we have been able to obtain crystal structures to identify the binding mode of these compounds. This allowed for rapid progression of the initial, weak binding, fragment starting points to compounds 37 and 38, which have 19F‐pKi values of 5.3 and 5.4 respectively.
Prognostic impact of number of induction courses to attain complete remission in patients with acute myeloid leukemia transplanted with either a matched sibling or human leucocyte antigen 10/10 or 9/10 unrelated donor: An Acute Leukemia Working Party European Society for Blood and Marrow Transplantation study
Authors: Loke Justin , Labopin Myriam , Craddock Charles , Socié Gérard , Gedde‐Dahl Tobias , Blaise Didier , Forcade Edouard , Salmenniemi Urpu , Huynh Anne , Versluis Jurjen , Yakoub‐Agha Ibrahim , Labussière‐Wallet Hélène , Maertens Johan , Passweg Jakob , Bulabois Claude Eric , Gabellier Ludovic , Mielke Stephan , Castilla‐Llorente Cristina , Deconinck Eric , Brissot Eolia , Nagler Arnon , Ciceri Fabio , Mohty Mohamad
Published: April 2024

Introduction

For the majority of patients with acute myeloid leukemia (AML) an allogeneic stem cell transplant (SCT) in first complete remission (CR) is preferred. However, whether the number of courses required to achieve CR has a prognostic impact is unclear. It is unknown which factors remain important in patients requiring more than one course of induction to attain remission.

Methods

This Acute Leukaemia Working Party study from the European Society for Blood and Marrow Transplantation identified adults who received an allograft in first CR from either a fully matched sibling or 10/10 or 9/10 human leucocyte antigen (HLA)‐matched unrelated donor (HLA‐A, HLA‐B, HLA‐C, HLA‐DR, or HLA‐DQ). Univariate and multivariate analyses were undertaken to identify the prognostic impact of one or two courses of induction to attain CR.

Results

A total of 4995 patients were included with 3839 (77%) patients attaining a CR following one course of induction chemotherapy (IND1), and 1116 patients requiring two courses (IND2) to attain CR. IND2 as compared to IND1 was a poor prognostic factor in a univariate analysis and remained so in a multivariate Cox model, resulting in an increased hazard ratio of relapse (1.38; 95% confidence interval [CI], 1.16–1.64; p = .0003) and of death (1.27; 95% CI, 1.09–1.47; p = .002). Adverse prognostic factors in a multivariate analysis of the outcomes of patients requiring IND2 included age, FLT3‐ITD, adverse cytogenetics, and performance status. Pretransplant measurable residual disease retained a prognostic impact regardless of IND1 or IND2.

Conclusion

Initial response to chemotherapy as determined by number of courses to attain CR, retained prognostic relevance even following SCT in CR.