bluuebunny/crossref_metadata_2025 huggingface dataset:
Development of the Power Assist System for High Efficiency and Lightweight Wearable Robot in Unstructured Battlefield
Authors: Park Huichang
Published: August 2023

The wearable robot system is designed to assist human skeletal and muscular systems for enhancing user’s abilities in various fields, including medical, industrial, and military. The military has an expanding need for wearable robots with the integration of surveillance/control systems and advanced equipment in unstructured battlefield environments. However, there is a lack of research on the design and mechanism of wearable robots, especially for power assist systems. This study proposes a lightweight wearable robot system that provides comfortable wear and muscle support effects in various movements for soldiers performing high-strength and endurance missions. The Power assist mechanism is described and verified, and the tasks that require power assist are analyzed. This study explain the system including its driving mechanism, control system, and mechanical design. Finally, the performance of the robot is verified through experiments and evaluations, demonstrating its effectiveness in muscle support.
Static Ejection Test for Separation Analysis of 2,000lb-Class Store
Authors: Shin Byungjoon , Jo Young-hee , Kim Min-soo
Published: August 2023

Static ejection tests were conducted using the 2,000lb-Class Store to provide ejector model for the store separation simulation. In this study, static ejection test device for 2,000lb-class store was constructed and reaction force applied to store was measured over time. In addition, the trajectories of the ejected store were obtained using photogrammetry and compared with the simulations using developed ejector model. The results of the static ejection test were analyzed to determine the cartridge-orifice combination to be used for store separation. Flight tests were performed by applying the analysis results and verified that the store was safely separated from the aircraft.
Two Circle-based Aircraft Head-on Reinforcement Learning Technique using Curriculum
Authors: Hwang Insu , Bae Jungho
Published: August 2023

Recently, AI pilots using reinforcement learning are developing to a level that is more flexible than rule-based methods and can replace human pilots. In this paper, a curriculum was used to help head-on combat with reinforcement learning. It is not easy to learn head-on with a reinforcement learning method without a curriculum, but in this paper, through the two circle-based head-on air combat learning technique, ownship gradually increase the difficulty and become good at head-on combat. On the two-circle, the ATA angle between the ownship and target gradually increased and the AA angle gradually decreased while learning was conducted. By performing reinforcement learning with and w/o curriculum, it was engaged with the rule-based model. And as the win ratio of the curriculum based model increased to close to 100 %, it was confirmed that the performance was superior.
Representation of Race and Ethnicity in the Contemporary US Health Cohort All of Us Research Program
Authors: Kathiresan Nina , Cho So Mi Jemma , Bhattacharya Romit , Truong Buu , Hornsby Whitney , Natarajan Pradeep
Published: August 2023

Importance

To address systemic disparities in biomedical research, the All of Us (AoU) Research Program was created to identify the root causes and consequences of health outcomes in the US. However, the extent of AoU’s racial and ethnic diversity is unknown.

Objective

To quantify representation of key racial and ethnic groups in the accruing AoU nationwide health cohort and compare with their actual representation in the US.

Design, Setting, and Participants

This cohort study compared the AoU program from May 2017 to June 2022 for individuals 18 years and older with the Decennial Survey 2020 (DEC) collected by the US Census Bureau.

Exposures

Representation of non-Hispanic Asian, non-Hispanic Black or African American, Hispanic or Latino, non-Hispanic White, and uncategorized or multiple races in AoU.

Main Outcomes and Measures

The extent of underrepresentation or overrepresentation of each racial group in the AoU program at both nationwide and state-level relative to DEC.

Results

Of the 358 705 US adults in the AoU to date, individuals identified with the following race and ethnicity categories: 12 710 non-Hispanic Asian (3.5%), 73 348 non-Hispanic Black or African American (20.5%), 58 488 Hispanic or Latino (16.3%), 205 457 non-Hispanic White (57.3%), and 8702 uncategorized or reporting multiple categories (2.4%). Of 355 413 participants with available sex at birth and age data, 218 981 (61.6%) were female and had a mean (SD) age of 53.1 (17.0) years, 136 037 (38.28%) were male and had a mean (SD) age of 56.7 (17.0) years, and 395 reported nonbinary sex (0.1%), with a mean (SD) age of 55.4 (15.8) years. Compared with the referent US, non-Hispanic Black or African American individuals were overrepresented in the AoU by 8.73% (AoU, 20.5% [73 348 of 358 705] vs DEC, 11.7% [30 266 080 of 258 343 281]) and by relative scale, 1.94-fold. Non-Hispanic White individuals accounted for the greatest participation in the AoU with generally consistent dominance across all regions yet numerically underrepresented by absolute difference of −3.54% (95% CI, −3.70 to −3.38). Uncategorized or multiracial group in the AoU (2.4% [8702 of 358 705]) was 0.43-fold likely to be represented relative to the DEC (4.6% [11 922 096 of 258 343 281]) with an absolute difference of −2.19% (95% CI, −2.24 to −2.14). Moreover, non-Hispanic Asian individuals were underrepresented by −2.54% (95% CI, −2.60 to −2.48) prominently in most states. Individuals identifying as Hispanic or Latino were nominally underrepresented by −0.46% (95% CI, −0.58 to −0.34) (AoU, 16.3% [58 488 of 358 705] vs DEC, 16.8% [43 322 792 of 258 343 281]).

Conclusions and Relevance

Recruitment trends for the ongoing AoU show relatively improved representation of some major race groups with geographic trends. These findings underscore the need to further tailor and augment recruitment and participation initiatives for diverse populations.
Paternal Depression and Risk of Depression Among Offspring
Authors: Dachew Berihun , Ayano Getinet , Duko Bereket , Lawrence Blake , Betts Kim , Alati Rosa
Published: August 2023

Importance

Existing epidemiological evidence is equivocal as to whether paternal depression poses a consequent risk of depression in offspring; meta-analysis of findings can help inform preventative intervention efforts.

Objective

To conduct a systematic review and meta-analysis of observational studies examining the association between paternal and offspring depression.

Data Sources

Embase, PubMed, PsycINFO, Scopus, and Web of Science databases were searched between inception and December 2022.

Study Selection

The review included all observational studies that investigated the association between paternal and offspring depression and 10 606 studies were initially identified.

Data Extraction and Synthesis

This systematic review and meta-analysis was performed following the Preferred Reporting Items for Systematic Review and Meta-analysis guidelines. The review protocol was prospectively registered in PROSPERO. Summary odds ratios (ORs) and 95% CIs were pooled using inverse variance weighted random effect meta-analysis. Subgroup and sensitivity analyses were performed.

Main Outcomes and Measures

The main outcome of interest was offspring depression measured using recognized depression assessment tools.

Results

Sixteen observational studies published between 2002 and 2021 were included, with a combined sample of 7 153 723 father-child dyads. A meta-analysis of these studies showed that paternal depression was associated with an increased risk of depression in offspring (OR, 1.42; 95% CI, 1.17-1.71). The risk was higher among offspring exposed to paternal depressive disorders (OR, 1.65; 95% CI, 1.28-2.12) than those exposed to depression as defined by a nonclinical symptom scale (OR, 1.12; 95% CI, 1.06-1.19). Sensitivity analysis revealed consistent pooled estimates ranging from 1.35 (95% CI, 1.12-1.62) to 1.45 (95% CI, 1.18-1.78).

Conclusions and Relevance

Paternal depression was associated with subsequent offspring depression. This finding shows the intergenerational transmission of mental health problems and suggests that mental health interventions benefit not only the patient but also the family as a whole, including both parents.
Prevalence and Factors Associated With Vaping Cannabidiol Among US Adolescents
Authors: Dai Hongying Daisy , Subramanian Roma , Mahroke Avina , Wang Ming
Published: August 2023

Importance

e-Cigarette use and vaping marijuana (cannabis) are popular among US adolescents. Cannabidiol (CBD) is a compound found in the cannabis plant that has recently increased in use.

Objectives

To examine the prevalence of and factors associated with youths vaping CBD.

Design, Setting, and Participants

This cross-sectional study included a nationally representative sample of students from middle and high schools (typical age, 11-18 years) in the US from the 2022 National Youth Tobacco Survey, conducted from January to May 2022.

Exposure

Demographic characteristics, harm perception of tobacco use, and vaping behaviors.

Main Outcomes and Measures

The main outcomes were weighted prevalence and population estimates of ever and current (past 30-day) vaping of CBD overall and by e-cigarette use status. Multivariable logistic regression analyses were conducted to estimate the association of currently vaping CBD with demographic factors and e-cigarette and tobacco use behaviors stratified by current e-cigarette use status.

Results

The study included 28 291 participants (51.1% male; mean [SD] age, 14.5 [2.0] years). Among 2448 current e-cigarette users, 21.3% (95% CI, 18.4%-24.1%) reported any past-month vaping of CBD and 6.3% (95% CI, 4.7%-7.8%) reported that they did not know whether they had vaped CBD. Hispanic e-cigarette users were more likely than their non-Hispanic White peers to report currently vaping CBD (adjusted odds ratio [AOR], 1.9; 95% CI, 1.3-2.8). Current e-cigarette users with higher frequency (≥20 days vs ≤5 days) and longer duration (2-3 years or >3 years vs <1 year) of use were more likely to report currently vaping CBD (frequency: AOR, 1.5 [95% CI, 1.1-1.9]; 2-3 years: AOR, 2.2 [95% CI, 1.2-3.9]; 3 years: AOR, 3.2 [95% CI, 1.7-6.1]). Among 25 091 noncurrent e-cigarette users, 1.2% (95% CI, 1.0%-1.5%) reported currently vaping CBD and 2.3% (95% CI, 2.1%-2.6%) reported that they did not know. High school students (vs middle school students; AOR, 4.2; 95% CI, 2.8-6.1) and gay or lesbian (AOR, 2.9; 95% CI, 1.6-5.4) or bisexual (AOR, 2.7; 95% CI, 1.8-4.0) (vs heterosexual) youths were more likely to report vaping CBD, while those who perceived tobacco as dangerous (vs not dangerous; AOR, 0.4; 95% CI, 0.3-0.6) had lower odds of reporting vaping CBD.

Conclusions and Relevance

In this cross-sectional study of US middle and high school students, the prevalence of youths vaping CBD was high, particularly among e-cigarette users and Hispanic and sexual minority populations. The findings suggest that evidence-based educational campaigns, interventions, and public policy changes are needed to reduce the harmful health outcomes possible with vaping CBD among developing youths.
Phagophore closure, autophagosome maturation and autophagosome fusion during macroautophagy in the yeast Saccharomyces cerevisiae
Authors: Kraft Claudine , Reggiori Fulvio
Published: August 2023

Macroautophagy, hereafter referred to as autophagy, is a complex process in which multiple membrane‐remodeling events lead to the formation of a cisterna known as the phagophore, which then expands and closes into a double‐membrane vesicle termed the autophagosome. During the past decade, enormous progress has been made in understanding the molecular function of the autophagy‐related proteins and their role in generating these phagophores. In this Review, we discuss the current understanding of three membrane remodeling steps in autophagy that remain to be largely characterized; namely, the closure of phagophores, the maturation of the resulting autophagosomes into fusion‐competent vesicles, and their fusion with vacuoles/lysosomes. Our review will mainly focus on the yeast Saccharomyces cerevisiae, which has been the leading model system for the study of molecular events in autophagy and has led to the discovery of the major mechanistic concepts, which have been found to be mostly conserved in higher eukaryotes.
Remote Administration of Physical and Cognitive Performance Assessments in a Predominantly Black Cohort of Persons With Systemic Lupus Erythematosus
Authors: Hoge Courtney , Bowling C. Barrett , Dunlop‐Thomas Charmayne , Pearce Brad D. , Drenkard Cristina , Lim S. Sam , Plantinga Laura C.
Published: August 2023

Objective

In a study of physical and cognitive functioning among predominantly Black individuals with systemic lupus erythematosus (SLE), we compared remotely administered physical and cognitive performance assessments to those collected in person.

Methods

A subset of participants who completed an in‐person visit in our parent study from 2021 to 2022 (n = 30) were recruited to complete a second, remote visit within 28 days. Physical performance (measured by a modified Short Physical Performance Battery [SPPB]; range 0‐12; subscale ranges 0‐4; higher = better performance) and cognitive performance (episodic and working memory adjusted t‐scores, measured using NIH Toolbox) were measured at both visits. Mean scores were compared using paired t‐tests; intraclass correlation coefficients (ICCs) were obtained from two‐way mixed effects models. Linear and logistic models were used to estimate stratified associations between performance measures and related outcomes.

Results

Participants were primarily female (93.3%) and Black (93.3%). In‐person versus remote overall SPPB (8.76 vs. 9.43) and chair stand (1.43 vs. 1.90) scores were statistically significantly lower. t‐Scores for episodic memory (47.27 vs. 49.53) and working memory (45.37 vs. 47.90) were lower for in‐person versus remote visits. The ICC for overall SPPB indicated good agreement (0.76), whereas the ICCs for episodic (0.49) and working memory (0.57) indicated poor‐moderate agreement. Associations between assessments of performance with related outcomes were similar and did not statistically significantly differ by modality of visit.

Conclusion

To possibly expand and diversify pools of participants in studies of physical and cognitive performance in SLE, remote administration of assessments should be considered for future research.
A Novel PTH‐Related Peptide Combined With 3D Printed Macroporous Titanium Alloy Scaffold Enhances Osteoporotic Osseointegration
Authors: Wang Junwu , Chen Renxin , Ren Bin , Feng Qinyu , Li Beihai , Hao Zhuowen , Chen Tianhong , Hu Yingkun , Huang Yilong , Zhang Qi , Wang Yi , Huang Jinghuan , Li Jingfeng
Published: August 2023

Previous parathyroid hormone (PTH)‐related peptides (PTHrPs) cannot be used to prevent implant loosening in osteoporosis patients due to the catabolic effect of local sustained release. A novel PTHrP (PTHrP‐2) that can be used locally to promote osseointegration of macroporous titanium alloy scaffold (mTAS) and counteract implant slippage in osteoporosis patients is designed. In vitro, PTHrP‐2 enhances the proliferation, adhesion, and osteogenic differentiation of bone marrow‐derived mesenchymal stem cells (BMSCs) within the mTAS. Further, it promotes proliferation, migration, angiogenesis‐related protein expression, and angiogenesis in human umbilical vein endothelial cells (HUVECs). Compared to PTH(1–34), PTHrP‐2 can partially weaken the osteoclast differentiation of RAW 264.7 cells. Even in an oxidative stress microenvironment, PTHrP‐2 safeguards the proliferation and migration of BMSCs and HUVECs, reduces reactive oxygen species generation and mitochondrial damage, and partially preserves the angiogenesis of HUVECs. In the Sprague–Dawley (SD) rat osteoporosis model, the therapeutic benefits of PTHrP‐2‐releasing mTAS (mTASP2) and ordinary mTAS implanted for 12 weeks via micro‐CT, sequential fluorescent labeling, and histology are compared. The results demonstrate that mTASP2 exhibits high bone growth rate, without osteophyte formation. Consequently, PTHrP‐2 exhibits unique local synthesis properties and holds the potential for assisting the osseointegration of alloy implants in osteoporosis patients.
Substrate Reshaping for Optically Tuned Liquid‐Printed Microlenses Beyond Their Wetting Properties
Authors: Martí Jerez Ernest , Fernández Pradas J. Marcos , Serra Pere , Duocastella Martí
Published: August 2023

Several strategies exist capable of fabricating microlenses for applications such as cameras and solar cells. Among them, techniques based on printing curable liquid prepolymers including inkjet and electrohydrodynamic‐jet printing, or laser‐induced forward‐transfer (LIFT) offer unique advantages in terms of ease of integration, cost, and compatibility with flexible substrates. However, the optical properties of the so‐fabricated microlenses depend on the wettability of the liquid prepolymer, preventing the broad implementation of printing technologies for micro‐optics. Herein, how printing microdroplets on top of reconfigurable substrates allows overcoming this issue is reported. The strategy, called print‐n‐release, is based on depositing prepolymer microdroplets on top of mechanically stretched elastomeric substrates. Once the stress applied to the substrate is released, and provided pinning of the contact line, the microdroplet's base diameter decreases producing an increase in contact angle and reduction in radius of curvature. Following a curing step, the microdroplets are converted into microlenses whose shape no longer depends exclusively on their wetting properties, but also on the substrate elongation. It is demonstrated that, by combining LIFT with substrates elongated up to 80%, microlenses can be fabricated with a 400% increase in contact angle and a 90% reduction in focal length, in good agreement with theoretical predictions.
Copper‐Mediated C−H Chalcogenation of Heterocycles: Application to the Synthesis of Chalcogenoxanthones
Authors: Zhou Yunhao , Xu Yue , Zheng Tao , Huang Dongliang , Chen Jianyang , Wu Yongchang , Mei Ruhuai , Ma Wenbo
Published: August 2023

A copper‐mediated C(sp2)−H chalcogenation of heterocycles with readily available dichalcogenide, benzeneselenol and thiol is described. This protocol demonstrates scalability, good chemo‐ and regio‐selectivity, as well as broad functional group tolerance, which overall provides an accessible method to valuable aryl chalcogenides. The chalcogenated picolinamide products could be further transformed into selenoxanthones and thioxanthone scaffolds through intramolecular cyclization via a semi‐one pot process.
Mechanochemical Assisted Chemoselective and Stereoselective Hydrogen‐Bonding Catalyzed Addition of Dithiomalonates to Enones
Authors: Mała Żaneta A. , Janicki Mikołaj J. , Góra Robert W. , Konieczny Krzysztof A. , Kowalczyk Rafał
Published: August 2023

Dithiomalonates proved to be active nucleophiles in the stereoselective additions to chalcones, dienones, and en‐ynones affording the desired Michael adducts with moderate to good yield and enantioselectivities up to 98%. In contrast, the analogous dibenzyl malonate remained inactive. Bifunctional Cinchona squaramides secured the effective chirality transfer and the selectivity towards Michael adducts of various bisthiomalonates following the soft enolization approach. The thioester's nature impacted the reactivity and stability of the reactants or products. The reactions performed in solution led to the product, but it required prolonged time along with byproducts formation such as sulfa‐Michael adducts, thus limiting the applicability of more reactive dithioesters. On the contrary, the reactions performed under solvent‐free, ball milling conditions furnished adducts in substantially less time, with negligible or no byproduct generation. Therefore, the mechanochemical approach revealed to be an effective tool for supporting the hardly effective reactions under standard solution conditions. The conducted comprehensive KS‐DFT studies are in line with the experimental observations shedding more light on the intricate active nucleophile formation at a molecular level and different chemical reaction pathways, as well as indicating the crucial transitions state governing the observed stereoselectivities.
Dual Photosensitizer Cycles Working Synergistically in a C(sp)‐C(sp3) Cross‐Coupling Reaction**
Authors: Bryden Megan Amy , Villa Marco , Fermi Andrea , Ceroni Paola , Zysman‐Colman Eli
Published: August 2023

To assess the value and reactivity of new photocatalysts (PCs), their performance should be evaluated in one or more established reactions and benchmarked against the performance using known PCs. Here, we evaluated our recently developed PC, pDTCz‐DPmS, in a C(sp)‐C(sp3) cross‐coupling reaction that had been documented in the literature. Previous findings indicated this reaction could not proceed in the absence of PC; however, under our conditions this was not the case. Without PC, a moderate product yield was obtained, while this yield increased significantly upon addition of pDTCz‐DPmS. UV‐Vis absorption studies indicated that the Hantzsch ester (HE) additive was acting as a competitive absorber of the light from the excitation source, and quenching studies confirmed that the HE was quenched by the radical precursor, N‐(acyloxy)phthalimide. Mechanistic investigations established that two parallel photosensitization pathways were in operation; a reductive quenching photocatalytic pathway (using pDTCz‐DPmS) and a sacrificial photoreductant pathway (employing HE). These pathways work synergistically to enhance the yield of target product.
Electron‐Poor Acridones and Acridiniums as Super Photooxidants in Molecular Photoelectrochemistry by Unusual Mechanisms
Authors: Žurauskas Jonas , Boháčová Soňa , Wu Shangze , Butera Valeria , Schmid Simon , Domański Michał , Slanina Tomáš , Barham Joshua P.
Published: August 2023

Electron‐deficient acridones and in situ generated acridinium salts are reported as potent, closed‐shell photooxidants that undergo surprising mechanisms. When bridging acyclic triarylamine catalysts with a carbonyl group (acridones), this completely diverts their behavior away from open‐shell, radical cationic, ‘beyond diffusion’ photocatalysis to closed‐shell, neutral, diffusion‐controlled photocatalysis. Brønsted acid activation of acridones dramatically increases excited state oxidation power (by +0.8 V). Upon reduction of protonated acridones, they transform to electron‐deficient acridinium salts as even more potent photooxidants (*E1/2=+2.56–3.05 V vs SCE). These oxidize even electron‐deficient arenes where conventional acridinium salt photooxidants have thusfar been limited to electron‐rich arenes. Surprisingly, upon photoexcitation these electron‐deficient acridinium salts appear to undergo two electron reductive quenching to form acridinide anions, spectroscopically‐detected as their protonated forms. This new behaviour is partly enabled by a catalyst preassembly with the arene, and contrasts to conventional SET reductive quenching of acridinium salts. Critically, this study illustrates how redox active chromophoric molecules initially considered photocatalysts can transform during the reaction to catalytically active species with completely different redox and spectroscopic properties.
Biomimetic Approach to Diverse Coral Diterpenes from a Biosynthetic Scaffold
Authors: Scesa Paul D. , Schmidt Eric W.
Published: August 2023

Thousands of coral terpenes originate from simple scaffolds that undergo oxidative tailoring. While corals are excellent sources of drug leads, the challenge of supplying structurally complex drug leads from marine organisms has sometimes slowed their development. Making this even more challenging, in comparison to other organisms, such as plants and microbes, for which the terpene literature is substantial, very little is known about how the unique coral terpenes are biosynthesized and elaborated in nature. In this study, we used a semisynthetic strategy to produce at gram scale in yeast the eunicellane scaffold that underlies >200 coral compounds. Synthetic oxidation reactions were explored, generating key scaffolds that reflect three of the four structural classes derived from eunicellane and enabling the first asymmetric syntheses of the natural products solenopodin C and klysimplexin Q. Biomimetic methods and detailed mechanistic studies of synthetic reactions shed light on potential enzymological reactivity, including the role of epoxide rearrangement in eunicellane biosynthesis.
Intermolecular Formal Cycloaddition of Indoles with Bicyclo[1.1.0]butanes by Lewis Acid Catalysis
Authors: Ni Dongshun , Hu Sai , Tan Xiangyu , Yu Yang , Li Zhenghua , Deng Li
Published: August 2023

Herein, we develop a new approach to directly access architecturally complex polycyclic indolines from readily available indoles and bicyclo[1.1.0]butanes (BCBs) through formal cycloaddition promoted by commercially available Lewis acids. The reaction proceeded through a stepwise pathway involving a nucleophilic addition of indoles to BCBs followed by an intramolecular Mannich reaction to form rigid indoline‐fused polycyclic structures, which resemble polycyclic indole alkaloids. This new reaction tolerated a wide range of indoles and BCBs, thereby allowing the one‐step construction of various rigid indoline polycycles containing up to four contiguous quaternary carbon centers.
Relationship between the deterioration of bleachability index (DOBI) value and hydrogenation performance for the hydrogenation of split‐crude palm oil (s‐CPO) in the oleochemical industry
Authors: Wong Farng Hui , Lim Mitchell S. W. , Tiong Timm Joyce , Chan Yi Jing , Asli Umi Aisah , Yap Yeow Hong
Published: August 2023

A major cause of premature catalyst deactivation in the catalytic hydrogenation of fatty acids is the presence of impurities in the feedstock. With more oleochemical plants shifting to opportunistic crude palm oil (CPO) as their feedstock, the feedstock quality becomes an important factor in their procurement process. For CPO, the impurities level can be coarsely estimated by the deterioration of bleaching index (DOBI). A high DOBI value (e.g. DOBI > 2.99) indicates good quality CPO and ease in processing, while low DOBI value implies low level of carotene and/or high level of oxidised sludge oil, both of which could be detrimental to the processing of CPO. In our work, unsplit CPO feedstocks with varying DOBI value were directly hydrogenated in a laboratory‐scale pressure reactor with the presence of commercial nickel catalysts. Experimental results showed that catalyst deactivation was linked to DOBI value, where decreasing DOBI led to faster catalyst deactivation. For example, iodine value (IV) < 1.0 can be achieved for CPO with high DOBI value (2.97) after 150 min, and IV of 5–7 and IV > 20 were achieved for medium DOBI value (2.57–2.68) and low DOBI value (2.24), respectively. For CPO with low DOBI value (2.24), doubling the catalyst dosage ensured that the hydrogenated product met the low IV specification. This work showed that identifying the CPO with DOBI value presents an indicator to the manufacturer to find the right CPO tailored to the existing processes to maximise profitability.
A collaborative approach to promote use of 3D printing in a biology research laboratory
Authors: Wong‐Welch Jenny , Cripps Richard M.
Published: August 2023

Three dimensional (3D) design and printing are customizable and cost‐effective approaches to developing small equipment and other items for use in various interdisciplinary applications. However, many pedagogical approaches to 3D printing focus more on the generation of artifacts than on the involvement of students as creators. Moreover, library makerspaces offer 3D printing services but cannot always engage the students with practical applications of their designs. We sought to determine if promoted use of 3D printing could be developed in biology laboratory trainees, ranging from undergraduate students to postdoctoral fellows. We combined two instructional workshops in the San Diego State University Library build IT makerspace, with two individual assignments to build items for the research laboratory. Evaluation of the course revealed that participants had expected the design and print processes to be of high complexity, but learned that the necessary skills could be acquired and applied in a relatively short period of time. Also, we found that trainees became proficient in 3D design and printing, and that a majority of individuals used 3D printing for subsequent applications. This effective translation of 3D printing to the research laboratory can be a paradigm for how 3D fabrication is taught. Moreover, this approach required the collaboration of library makerspace and research faculty, underlining the value of embedded librarianship in enhancing training and knowledge.
Exploring Photoswitchable Binding Interactions with Small‐Molecule‐ and Peptide‐Based Inhibitors of Trypsin
Authors: Palasis Kathryn A. , Peddie Victoria , Turner Dion J. L. , Zhang Xiaozhou , Yu Jingxian , Abell Andrew D.
Published: August 2023

The ability to photochemically activate a drug, both when and where needed, requires optimisation of the difference in biological activity between each isomeric state. As a step to this goal, we report small‐molecule‐ and peptide‐based inhibitors of the same protease—trypsin—to better understand how photoswitchable drugs interact with their biological target. The best peptidic inhibitor displayed a more than fivefold difference in inhibitory activity between isomeric states, whereas the best small‐molecule inhibitor only showed a 3.4‐fold difference. Docking and molecular modelling suggest this result is due to a large change in 3D structure in the key binding residues of the peptidic inhibitor upon isomerisation; this is not observed for the small‐molecule inhibitor. Hence, we demonstrate that significant structural changes in critical binding motifs upon irradiation are essential for maximising the difference in biological activity between isomeric states. This is an important consideration in the design of future photoswitchable drugs for clinical applications.
The Role of Trp79 in β‐Actin on Histidine Methyltransferase SETD3 Catalysis
Authors: Al‐Fakhar Mays S. Q. , Bilgin Nurgül , Moesgaard Laust , Witecka Apolonia , Drozak Jakub , Kongsted Jacob , Mecinović Jasmin
Published: August 2023

Nτ‐methylation of His73 in actin by histidine methyltransferase SETD3 plays an important role in stabilising actin filaments in eukaryotes. Mutations in actin and overexpression of SETD3 have been related to human diseases, including cancer. Here, we investigated the importance of Trp79 in β‐actin on productive human SETD3 catalysis. Substitution of Trp79 in β‐actin peptides by its chemically diverse analogues reveals that the hydrophobic Trp79 binding pocket modulates the catalytic activity of SETD3, and that retaining a bulky and hydrophobic amino acid at position 79 is important for efficient His73 methylation by SETD3. Molecular dynamics simulations show that the Trp79 binding pocket of SETD3 is ideally shaped to accommodate large and hydrophobic Trp79, contributing to the favourable release of water molecules upon binding. Our results demonstrate that the distant Trp79 binding site plays an important role in efficient SETD3 catalysis, contributing to the identification of new SETD3 substrates and the development of chemical probes targeting the biomedically important SETD3.
Characterization of prolamin storage protein profiles in Tunisian pearl millet landraces toward better utilization and improvement
Authors: Ben‐Romdhane Mériam , Riahi Leila , Borji Manel , Riahi Jawaher , Chibani Farhat , Ghorbel Abdelwahed , Zoghlami Nejia
Published: August 2023

Background and Objectives

This study reports for the first time the variation of prolamin profiles among 51 pearl millet landraces representing seven populations prospected from contrasted bioclimatic areas of Tunisia.

Findings

A total of 27 prolamins bands were detected, ranging from 11 to 245 kDa. Among them, 14 were polymorphic, resulting in a polymorphism rate of 51.85%. The bands with lower molecular weights are the most frequent. The biochemical marker M25.4 showed the highest value of Nei genetic diversity (h = 0.500), Shannon information index (I = 0.693), and effective number of alleles per locus Ne (2). At the population level, the polymorphism rates ranged between 50% (Mahdia) and 92.86% (Hammem Jebli, Kairouan, Medenine). The population of Kairouan showed the highest genetic diversity indices (I = 0.511 ± 0.054, h = 0.345 ± 0.041), while the lowest levels were recorded for the population of Mahdia (I = 0.268 ± 0.076, h = 0.177 ± 0.052). Analysis of molecular variance analysis indicated that the highest amount of genetic diversity was encompassed within the studied populations (89%). This was supported by low genetic differentiation (PhiPT = 0.110, p = .029) and Nei genetic distance values. The classification pattern using ward dendrogram and factorial analyses revealed the distinction of two clusters with a low genetic structure based on the geographic origins of landraces.

Significance and Novelty

The detected biochemical protein polymorphism could be a highly effective tool for the genetic resources characterization of pearl millet landraces, which will be further utilized in breeding investigations and taxonomic surveys of this cereal crop.
Mitral valve replacement with annuloplasty in a patient with infected mitral annular calcification
Authors: Horibe Tatsuya , Hidaka Hideaki , Numaguchi Ryosuke , Takaki Jun , Nishigawa Kosaku , Yoshinaga Takashi , Fukui Toshihiro
Published: August 2023

Key Clinical Message

Extensive resection of the infected calcified annulus and the reconstruction with a pericardial patch for the debrided annulus is an effective surgical option for the treatment of infectious endocarditis in patients with mitral annular calcification.

A 78‐year‐old woman was referred to our hospital because of left‐sided hemiparesis. During the treatment for cerebral infarction, the patient became feverish and lost consciousness. Transthoracic echocardiography revealed mitral annular calcification and a tumor‐like mass on the posterior leaflet despite no findings of mitral regurgitation. She underwent successful mitral valve replacement with debridement of the infected mitral annulus and reconstruction of the posterior annulus (annuloplasty) with bovine pericardium after removal of the mitral annular calcification.
A Dinuclear Re Complex as a Multi Talent – Photocatalysis and Electrocatalysis combined with Spectroscopy
Authors: Obermeier Martin , Caliskanyuerek Volkan , Lomlu Rana , Giereth Robin , Cula Beatrice , Tschierlei Stefanie , Schwalbe Matthias
Published: August 2023

Mononuclear rhenium complexes have been widely studied as photo‐ and electrocatalysts. However, dinuclear systems with cooperative properties have rarely been investigated. On the basis of two homobimetallic rhenium complexes, we report the synthesis and characterization of two isomers and their photo‐ and electrochemical properties. By combining the respective isomer with the photosensitizer [Ir(dFppy)3] (Ir, dFppy=2‐(4,6‐difluorophenyl) pyridine)) enhanced CO2 to CO transformation could be observed and by further spectroscopic investigations the reaction mechanism could be fathomed. The observed enhanced catalytic activity compared to monometallic systems derives from the cooperative Re−Re interaction through two electron reduction on the complex (and thereby formation of an intermediate species with a Re−Re bond). Using LSV measurements the cooperative CO2 activation was also observed for one of the isomers, cisL1‐Re2Cl2, in electrocatalytic measurements. The two isomers have a somewhat lower catalytic activity than earlier prepared geometric isomers, but show better catalytic properties than their mononuclear counterpart.
Continuous Reactive Crystallization in a Mesoscale Oscillatory Baffled Reactor
Authors: Ahmed Safaa M. R. , Walton David , Gheni Saba A. , Phan Anh N.
Published: August 2023

Continuous reactive crystallization was carried out in a mesoscale oscillatory baffled reactor (meso‐OBR), using calcium carbonate as a case study to demonstrate the ability of high solid loadings and to examine the fouling potential in continuous processes. Plug flow behavior was easily achieved in reactive solid‐liquid phase reaction systems, as evidenced by the rapid establishment of a steady state. Effects of the operating conditions (reactant concentration, mixing conditions, and temperature) on the yield, particle size, and particle size distribution were studied. Increasing the reactant concentration and oscillation conditions reduced the particle size whereas increasing the operating temperature led to a large particle size. The meso‐OBR produced uniformly shaped spherical crystals, with a 35 % reduction in average particle size and high purity compared to conventional stirred tanks. The meso‐OBR could be used continuously for up to 6 h with less than 1 wt % of fouling (product loss).
Supercritical Methanol and Ethanol Solubility Estimation by Using Molecular Dynamics Simulation
Authors: Moradi Hojatollah , Azizpour Hedayat , Khadiv-Parsi Parissa , Ghorbani Nia Reyhane
Published: August 2023

Solubility plays a crucial role in arranging extraction operations. Among solvents, supercritical methanol and ethanol have distinct extraction applications; thus, investigating their solubility parameters is crucial. This study investigates the solubility parameters of supercritical methanol and ethanol using molecular dynamics simulation at variable temperatures and pressures. The predicted solubility parameters for the solvents match the theoretical data. In this case, the root mean square error values for supercritical methanol and sub‐/supercritical ethanol were 0.6934 and 1.0643, respectively. To realize the electrostatic and van der Waals interactions, the Ewald and atom‐based summation methods were used, respectively. Also, this study shows that improving the density linearly enhances the solubility.
Photo‐Catalyzed α‐Arylation of Enol Acetate Using Recyclable Silica‐Supported Heteroleptic and Homoleptic Copper(I) Photosensitizers
Authors: Body Nathalie , Bevernaegie Robin , Lefebvre Corentin , Jabin Ivan , Hermans Sophie , Riant Olivier , Troian‐Gautier Ludovic
Published: August 2023

Earth‐abundant photosensitizers are highly sought after for light‐mediated applications, such as photoredox catalysis, depollution and energy conversion schemes. Homoleptic and heteroleptic copper(I) complexes are promising candidates in this field, as copper is abundant and the corresponding complexes are easily obtained in smooth conditions. However, some heteroleptic copper(I) complexes suffer from low (photo)stability that leads to the gradual formation of the corresponding homoleptic complex. Such degradation pathways are detrimental, especially when recyclability is desired. This study reports a novel approach for the heterogenization of homoleptic and heteroleptic Cu complexes on silica nanoparticles. In both cases, the photophysical properties upon surface immobilization were only slightly affected. Excited‐state quenching with aryl diazonium derivatives occurred efficiently (108–1010 M−1 s−1) with heterogeneous and homogeneous photosensitizers. Moderate but almost identical yields were obtained for the α‐arylation of enol acetate using the homoleptic complex in homogeneous or heterogeneous conditions. Importantly, the silica‐supported photocatalysts were recycled with moderate loss in photoactivity over multiple experiments. Transient absorption spectroscopy confirmed that excited‐state electron transfer occurred from the homogeneous and heterogeneous homoleptic copper(I) complexes to aryl diazonium derivatives, generating the corresponding copper(II) center that persisted for several hundreds of microseconds, compatible with photoredox catalysis applications.
Activation of the GaI Cation for Bond Activation: from Oxidative Additions into C−Cl and H−P Bonds to Reversible Insertion into P4
Authors: Dabringhaus Philipp , Heizmann Tim , Krossing Ingo
Published: August 2023

Although the discovery of the GaI complex salt [Ga(PhF)2‐3][Al(ORF)4] (RF=C(CF3)3, PhF=C6H5F) invoked the preparation of a diverse library of cationic Ga(I) coordination complexes and clusters, studies on small molecule activation with low‐valent GaI cations are scarce. Herein, a first experimental study on the reactivity of a monomeric Ga(I) cation activated with a pyridine–diimine pincer ligand (in [Ga(PDIdipp)][Al(ORF)4]) towards small‐molecules is reported. First controlled oxidative additions of the GaI cation into C−Cl, H−P and P−P bonds are presented. Moreover, the [4+1]cycloaddition to butadienes was achieved. Intriguingly, the isolated, blue insertion product into the P−P bond of P4 allows for the quantitative release of the P4 molecule upon reaction with AlEt3 and butadienes. Reversible P4 insertion of main‐group metals has previously been reported for Ge and Sn, respectively. The experimental study is supported by high‐level computational analysis of the in‐part reversible oxidative additions at the DLPNO‐CCSD(T)/def2‐TZVPP//PBEh‐3c/def2‐mSVP level of theory with COSMO‐RS solvation in 1,2‐difluorobenzene.
Vanadium(V) Pyridine‐Containing Schiff Base Catecholate Complexes are Lipophilic, Redox‐Active and Selectively Cytotoxic in Glioblastoma (T98G) Cells
Authors: Kostenkova Kateryna , Levina Aviva , Walters Drew A. , Murakami Heide A. , Lay Peter A. , Crans Debbie C.
Published: August 2023

Two new series of complexes with pyridine‐containing Schiff bases, [VVO(SALIEP)L] and [VVO(Cl‐SALIEP)L] (SALIEP=N‐(salicylideneaminato)‐2‐(2‐aminoethylpyridine; Cl‐SALIEP=N‐(5‐chlorosalicylideneaminato)‐2‐(2‐aminoethyl)pyridine, L=catecholato(2−) ligand) have been synthesized. Characterization by 1H and 51V NMR and UV‐Vis spectroscopies confirmed that: 1) most complexes form two major geometric isomers in solution, and [VVO(SALIEP)(DTB)] (DTB=3,5‐di‐tert‐butylcatecholato(2−)) forms two isomers that equilibrate in solution; and 2) tert‐butyl substituents were necessary to stabilize the reduced VIV species (EPR spectroscopy and cyclic voltammetry). The pyridine moiety within the Schiff base ligands significantly changed their chemical properties with unsubstituted catecholate ligands compared with the parent HSHED (N‐(salicylideneaminato)‐N′‐(2‐hydroxyethyl)‐1,2‐ethanediamine) Schiff base complexes. Immediate reduction to VIV occurred for the unsubstituted‐catecholato VV complexes on dissolution in DMSO. By contrast, the pyridine moiety within the Schiff base significantly improved the hydrolytic stability of [VVO(SALIEP)(DTB)] compared with [VVO(HSHED)(DTB)]. [VVO(SALIEP)(DTB)] had moderate stability in cell culture media. There was significant cellular uptake of the intact complex by T98G (human glioblastoma) cells and very good anti‐proliferative activity (IC50 6.7±0.9 μM, 72 h), which was approximately five times higher than for the non‐cancerous human cell line, HFF‐1 (IC50 34±10 μM). This made [VVO(SALIEP)(DTB)] a potential drug candidate for the treatment of advanced gliomas by intracranial injection.
Catalytic Inhibition of Base‐Mediated Reactivity by a Self‐Assembled Metal‐Ligand Host
Authors: da Camara Bryce , Woods Connor Z. , Sharma Komal , Wu Hoi‐Ting , Farooqi Naira S. , Chen Changwei , Julian Ryan R. , Vander Griend Douglas A. , Hooley Richard J.
Published: August 2023

Spacious M4L6 tetrahedra can act as catalytic inhibitors for base‐mediated reactions. Upon adding only 5 % of a self‐assembled Fe4L6 cage complex, the conversion of the conjugate addition between ethylcyanoacetate and β‐nitrostyrene catalyzed by proton sponge can be reduced from 83 % after 75 mins at ambient temperature to <1 % under identical conditions. The mechanism of the catalytic inhibition is unusual: the octacationic Fe4L6 cage increases the acidity of exogenous water in the acetonitrile reaction solvent by favorably binding the conjugate acid of the basic catalyst. The inhibition only occurs for Fe4L6 hosts with spacious internal cavities: minimal inhibition is seen with smaller tetrahedra or Fe2L3 helicates. The surprising tendency of the cationic cage to preferentially bind protonated, cationic ammonium guests is quantified via the comprehensive modeling of spectrophotometric titration datasets.
Promoting Electrocatalytic CO2 Reduction to CO via Sulfur‐Doped Co‐N‐C Single‐Atom Catalyst†
Authors: Wei Zhiming , Liu Yuhang , Ding Jie , He Qinye , Zhang Qiao , Zhai Yueming
Published: August 2023

Comprehensive Summary

Electrocatalytic reduction of CO2 to fuels and chemicals possesses huge potential to alleviate current environmental crisis. Heteroatom doping in metal‐nitrogen‐carbon (M‐N‐C) single‐atom catalysts (SACs) has been found to be capable to promote the electrocatalytic CO2 reduction reaction (CO2RR). However, the origin of the enhanced activity is still elusive. Here, we report that sulfur‐doped cobalt‐nitrogen‐carbon single‐atom catalyst (Co1‐SNC) exhibits superior CO2RR performance compared to sulfur‐free counterpart (Co1‐NC). On the basis of in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS), kinetic isotope effect (KIE) and theoretical calculation, it is demonstrated that sulfur doping can promote water activation, elevate the d‐band center of Co active site, and reduce the free energy of *COOH intermediate formation. This work deepens the understanding of the CO2RR chemistry over heteroatom‐doped SACs for designing efficient CO2RR processes.
Analysis of Dynamical Peculiarities in Nanoalloys at Subsystems Level: Dynamical Degrees of Freedom, Temperature Differences, and the Chameleon Effect
Authors: Aleinikava Darya , Jellinek Julius
Published: August 2023

A novel analysis of the dynamical behavior of nanoalloy systems, as represented by model Ni/Al 13‐atom clusters, over a broad range of energies that cover the stage‐wise transition of the systems from their solid‐like to liquid‐like state is presented. Conceptually, the analysis is rooted in partitioning the systems into judiciously chosen subsystems and characterizing the latter in terms of subsystem‐specific dynamical descriptors that include dynamical degrees of freedom, root‐mean‐square bond‐length fluctuation, and element‐specific subsystem temperature. The analysis reveals a host of intriguing new peculiarities in the dynamical behavior of the Ni/Al 13‐mers, among which are what we call the chameleon effect and the difference in the temperatures of the Ni and Al subsystems at high energies, a difference that strongly depends on the cluster composition and also changes with energy. These do not have an analog in pure Ni13 and Al13 and are explained in terms of the coupled effects of the difference between the masses of the Ni and Al atoms (the mass effect) and of the difference in the anharmonicity of the overall interaction potential as experienced by the Ni and Al subsystems of the clusters (the potential effect).
Investigating Possible Dipole‐Bound States of Cyanopolyynes: the Case for the C5N− Anion Detected in Interstellar Space
Authors: Jerosimić Stanka , Milovanović Milan , Mitić Marko , Wester Roland , Gianturco Francesco A.
Published: August 2023

We present results of quantum structure calculations aimed at demonstrating the possible existence of dipole‐bound states (DBS) for the anion
, a species already detected in the Interstellar medium (ISM). The positive demonstration of DBS existence using ab initio studies is an important step toward elucidating possible pathways for the formation of the more tightly bound valence bound states (VBS) in environments where free electrons from starlight ionization processes are known to be available to interact with the radical partner of the title molecule. Our current calculations show that such excited DBS states can exist in
, in agreement with what we had previously found for the smallercyanopolyyne in the series: the
anion. This system has a very weakly bound anion with binding energies of about 3 and 9 cm−1 for the
and
DBS, respectively.