bluuebunny/crossref_metadata_2025 huggingface dataset:
A Route to High Thermoelectric Performance: Solution‐Based Control of Microstructure and Composition in Ag2Se
Authors: Kleinhanns Tobias , Milillo Francesco , Calcabrini Mariano , Fiedler Christine , Horta Sharona , Balazs Daniel , Strumolo Marissa J. , Hasler Roger , Llorca Jordi , Tkadletz Michael , Brutchey Richard L. , Ibáñez Maria
Published: March 2024

Thermoelectric materials convert heat into electricity, with a broad range of applications near room temperature (RT). However, the library of RT high‐performance materials is limited. Traditional high‐temperature synthetic methods constrain the range of materials achievable, hindering the ability to surpass crystal structure limitations and engineer defects. Here, a solution‐based synthetic approach is introduced, enabling RT synthesis of powders and exploration of densification at lower temperatures to influence the material's microstructure. The approach is exemplified by Ag2Se, an n‐type alternative to bismuth telluride. It is demonstrated that the concentration of Ag interstitials, grain boundaries, and dislocations are directly correlated to the sintering temperature, and achieve a figure of merit of 1.1 from RT to 100 °C after optimization. Moreover, insights into and resolve Ag2Se's challenges are provided, including stoichiometry issues leading to irreproducible performances. This work highlights the potential of RT solution synthesis in expanding the repertoire of high‐performance thermoelectric materials for practical applications.
Who is willing to pay a premium for leafy greens produced by indoor agriculture? A comparative choice experiment with US consumers
Authors: Seong Joseph , Valle De Souza Simone , Athnos April , Peterson H. Christopher
Published: March 2024

Indoor agriculture (IA) presents a pathway to producing leafy greens more sustainably by strictly controlling the growing environment, increasing the efficiency of water and land resources use, reducing pesticide application, and enhancing quality characteristics. However, the commercial success of adopting this production method depends on the technology's widespread consumer acceptance paired with a price premium for the improved quality it provides. This paper characterizes American consumer preferences for leafy greens, reports a positive WTP for leafy green attributes, and estimates how consumer attitudes toward IA affect their leafy green choices. The findings are drawn from an online survey of over 2000 US leafy green consumers conducted in 2021. The respondents faced a hypothetical discrete choice experiment (DCE) designed to simulate purchasing leafy green produce. The alternatives presented in the DCE varied over production systems (IA, field farming, or greenhouses) and quality levels (taste, freshness, nutrient level, and food safety). Estimates identify significant preference heterogeneity for leafy green attributes and facilitate classifying consumers into three preference‐based groups: “Quality Seekers,” “Price Conscious,” and “Focused Practicals.” Preference variation is significantly greater for production methods than quality characteristics, indicating nascent production method preferences. Results suggest most US consumers view IA positively; however, WTP estimates vary significantly between consumer segments [EconLit Citations: D12, D13].
Humans (Homo sapiens) but not baboons (Papio papio) demonstrate crossmodal pitch‐luminance correspondence
Authors: Margiotoudi Konstantina , Fagot Joel , Meguerditchian Adrien , Dautriche Isabelle
Published: March 2024

Humans spontaneously and consistently map information coming from different sensory modalities. Surprisingly, the phylogenetic origin of such cross‐modal correspondences has been under‐investigated. A notable exception is the study of Ludwig et al. (Visuoauditory mappings between high luminance and high pitch are shared by chimpanzees [Pan troglodytes] and humans. Proceedings of the National Academy of Sciences, 108(51), 20661–20665) which reports that both humans and chimpanzees spontaneously map high‐pitched sounds with bright objects and low‐pitched sounds with dark objects. Our pre‐registered study aimed to directly replicate this research on both humans and baboons (Papio papio), an old world monkey which is more phylogenetically distant from humans than chimpanzees. Following Ludwig et al. participants were presented with a visual classification task where they had to sort black and white square (low and high luminance), while background sounds (low or high‐pitched tones) were playing. Whereas we replicated the finding that humans' performance on the visual task was affected by congruency between sound and luminance of the target, we did not find any of those effects on baboons' performance. These results question the presence of a shared cross‐modal pitch‐luminance mapping in other nonhuman primates.
Food insecurity: Discrepancy within Australian couple households
Authors: Fry Jane M. , Temple Jeromey B.
Published: March 2024

Food security remains a global public health priority but there may be bias in the prevalence of household food insecurity, depending upon who answers the questions. Using a cross‐section from the Household, Income and Labour Dynamics in Australia (HILDA) Survey, we analysed components of food insecurity reported separately by both partners in 718 households, allowing examination of discrepancies among couples. We modelled discrepancy in reports of food insecurity on 8 items using binary logit models for each question and a binomial regression for the number of questions on which there was discrepancy. Among couples who differed on an item, (conditional) discrepancy rates ranged from 71.75% to 85.86%. Females were more likely than males to report food insecurity on most items. Key characteristics associated with discrepancy were female's and male's age, female's education, being born in Australia, renting and male's employment. Male's age and birthplace were associated with discrepancy on more items while male's higher education and being a homeowner were associated with discrepancy on fewer items. Among couples who differed in responses, females were more likely to report food insecurity if they were older or had a disability, if their male partner was younger or had no disability, or if either person had more education than high school. The prevalence of food insecurity among couple households may be underestimated by 7.4 percentage points due to discrepancies in reporting. Discrepancies can reduce the accuracy of measures of food insecurity, impeding the targeting of responses, and lead to a less efficient allocation of resources to combat food insecurity.
The ‘onion skin’ sign of a low‐grade appendiceal mucinous neoplasm: An incidental finding during early pregnancy assessment
Authors: Fourie Hanine , Al Memar Maya , Tuomey Maeve , Stalder Catriona , Ziprin Paul , Bourne Tom
Published: March 2024

A low‐grade appendiceal mucinous neoplasm (LAMN) is a cystic dilatation of the appendix resulting from the accumulation of mucinous secretions caused by a luminal obstruction. Although usually benign, pseudomyxoma peritonei may occur in the event of rupture, and 10% of cases may be secondary to appendiceal cystadenocarcinoma. A LAMN is both more common and more likely to have a malignant association in women, making it an entity with which practitioners of gynaecological ultrasound should be familiar. Although not the primary aim, early pregnancy ultrasound assessments can offer the diagnostic opportunity to identify pelvic pathology. A LAMN can be identified on ultrasonography by visualisation of an adnexal mass separate to the ovary, which due to the layers of secretions has a distinctive appearance previously likened to ‘onion‐skin’ or ‘whipped‐cream’. Here, we describe an incidental finding of a LAMN during an early pregnancy assessment. Practitioners of early pregnancy ultrasound should be familiar with the characteristic morphology of this rare but important finding.
Splenic injury caused by cardiopulmonary resuscitation in a full stomach with hematoma after hemorrhagic shock due to bleeding duodenal ulcer: A case report
Authors: Fujimori Daisuke , Koyama Tomohide , Ooki Satomi , Ito Masaaki , Yoshiike Yasutaka , Nakamura Satoshi , Yoshida Ryuhei , Sakamoto So , Ito Chikao , Kasuya Miyuki , Oe Kyoji , Takahashi Isao
Published: March 2024

Background

Cardiopulmonary resuscitation is essential for cardiopulmonary arrest, but complications from chest compressions warrant monitoring. Although rib and sternal fractures are common, abdominal injuries are rare, and splenic injuries are much rarer.

Case Presentation

A 74‐year‐old man was admitted to the emergency room with a hemorrhagic duodenal ulcer. During hospitalization, the patient went into cardiopulmonary arrest due to hemorrhagic shock. Spontaneous circulation returned after 7 min of cardiopulmonary resuscitation. He underwent transcatheter arterial embolization to stop the bleeding from the duodenal ulcer. The next day, a close examination of the patient's progressive anemia revealed splenic injury; transcatheter arterial embolization was performed to save his life.

Conclusion

It is important to consider the complication of splenic injury in patients with cardiopulmonary arrest who have undergone appropriate cardiopulmonary resuscitation. A possible mechanism—especially in patients with a full stomach—is the squeezing of the spleen by the diaphragm, abdominal wall, and stomach.
Proximity Effects on the Reactivity of a Nonheme Iron (IV) Oxo Complex in C−H Oxidation
Authors: Fagnano Alessandro , Frateloreto Federico , Paoloni Roberta , Sappino Carla , Lanzalunga Osvaldo , Costas Miquel , Di Stefano Stefano , Olivo Giorgio
Published: March 2024

Precise control of substrate positioning and orientation (its proximity to the reactive unit) is often invoked to rationalize the superior enzymatic reaction rates and selectivities when compared to synthetic models. Artificial nonheme iron (IV) oxo (Fe(IV)=O) complexes react with C(sp3)−H bonds via a biomimetic Hydrogen Atom Transfer/Hydroxyl Rebound mechanism, but rates, site‐selectivity and even hydroxyl rebound efficiency (ligand rebound versus substrate radical diffusion) are smaller than in oxygenases. Herein, we quantitatively analyze how substrate binding modulates nonheme Fe(IV)=O reactivity by comparing rates and outcomes of C−H oxidation by a pair of Fe(IV)=O complexes that share the same first coordination sphere but only one contains a crown ether receptor that recognizes the substrate. Substrate binding makes the reaction intramolecular, exhibiting Michaelis–Menten kinetics and increased reaction rates. In addition, C−H oxidation occurs with high site selectivity for remote sites. Analysis of Effective Molarity reveals that the system operates at its maximal theoretical capability for the oxidation of these remote sites. Remarkably, substrate positioning also affects Hydroxyl Rebound, whose efficiency only increases on the sites placed in proximity by recognition. Overall, these observations provide evidence that supramolecular control of substrate positioning can effectively modulate the reactivity of oxygenases and its models.
The Influence of Light‐Generated Radicals for Highly Efficient Solar‐Thermal Conversion in an Ultra‐Stable 2D Metal‐Organic Assembly
Authors: Lan Wenlong , Gou Xiaoshuang , Wu Yuewei , Liu Ning , Lu Lele , Cheng Peng , Shi Wei
Published: March 2024

Solar‐thermal water evaporation is a promising strategy for clean water production, which needs the development of solar‐thermal conversion materials with both high efficiency and high stability. Herein, we reported an ultra‐stable cobalt(II)‐organic assembly NKU‐123 with light‐generated radicals, exhibiting superior photothermal conversion efficiency and high stability. Under the irradiation of 808 nm light, the temperature of NKU‐123 rapidly increases from 25.5 to 215.1 °C in 6 seconds. The solar water evaporator based on NKU‐123 achieves a high solar‐thermal water evaporation rate of 1.442 and 1.299 kg m−2 h−1 under 1‐sun irradiation with a water evaporation efficiency of 97.8 and 87.9 % for pure water and seawater, respectively. A detailed mechanism study revealed that the formation of light‐generated radicals leads to an increase of spin density of NKU‐123 for enhancing the photothermal effect, which provides insights into the design of highly efficient photothermal materials.
Unusual Stabilisation of Remarkably Bent Tetra‐Cationic Tetra‐radical Intermolecular Fe(III) μ‐Oxo Tetranuclear Complexes
Authors: Sarkar Sabyasachi , Tiwari Rupesh Kumar , Samanta Deepannita , Guchhait Tapas , Sañudo E. Carolina , Rajaraman Gopalan , Rath Sankar Prasad
Published: March 2024

A hitherto unknown series of air stable, π‐conjugated, remarkably bent tetra‐cation tetra‐radical intermolecular Fe(III) μ‐oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X‐ray structure determination of two such molecules. These species facilitate long‐range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six‐coordinate iron centres stabilise the admixed intermediate spin states while the central five‐coordinate iron centres stabilise the high‐spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)−O−Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π‐cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.
How to Deal with Charge in the Ranking of Lewis Acidity: Critical Evaluation of an Extensive Set of Cationic Lewis Acids
Authors: Erdmann Philipp , Schmitt Manuel , Sigmund Lukas M. , Krämer Felix , Breher Frank , Greb Lutz
Published: March 2024

The quantification of Lewis acidity is of fundamental and applied importance in chemistry. However, if neutral and charged Lewis acids are compared, a coherent ranking has been elusive, and severe uncertainties were accepted. With this study, we present a systematic computational analysis of Lewis base affinities of 784 mono‐, di‐ and tricationic Lewis acids and their comparison with 149 representative neutral Lewis acids. Evaluating vacuum fluoride ion affinities (FIA) reveals a charge‐caused clustering that prohibits any meaningful ranking. Instead, solvation‐corrected FIAsolv is identified as a metric that overcomes charge sensitivity in a balanced manner, allowing for a coherent evaluation of Lewis acidity across varying charge states. Analyzing the impact of molecular volume on solvation‐induced FIA damping provides rationales for fundamental trends and guidelines for the choice or design of neutral and cationic Lewis acids in the condensed phase. Exploring alternative scales, explicit counteranion effects, and selected experimental case studies reaffirms the advantages of solvation‐corrected FIAsolv as the most versatile and practical approach for the quantitative ranking of general (thermodynamic) Lewis acidity.
Metalloradical Catalysis: General Approach for Controlling Reactivity and Selectivity of Homolytic Radical Reactions
Authors: Lee Wan‐Chen Cindy , Zhang X. Peter
Published: March 2024

Since Friedrich Wöhler's groundbreaking synthesis of urea in 1828, organic synthesis over the past two centuries has predominantly relied on the exploration and utilization of chemical reactions rooted in two‐electron heterolytic ionic chemistry. While one‐electron homolytic radical chemistry is both rich in fundamental reactivities and attractive with practical advantages, the synthetic application of radical reactions has been long hampered by the formidable challenges associated with the control over reactivity and selectivity of high‐energy radical intermediates. To fully harness the untapped potential of radical chemistry for organic synthesis, there is a pressing need to formulate radically different concepts and broadly applicable strategies to address these outstanding issues. In pursuit of this objective, researchers have been actively developing metalloradical catalysis (MRC) as a comprehensive framework to guide the design of general approaches for controlling over reactivity and stereoselectivity of homolytic radical reactions. Essentially, MRC exploits the metal‐centered radicals present in open‐shell metal complexes as one‐electron catalysts for homolytic activation of substrates to generate metal‐entangled organic radicals as the key intermediates to govern the reaction pathway and stereochemical course of subsequent catalytic radical processes. Different from the conventional two‐electron catalysis by transition metal complexes, MRC operates through one‐electron chemistry utilizing stepwise radical mechanisms.
Nuclear Magnetic Resonance Chemical Shift as a Probe for Single‐Molecule Charge Transport
Authors: Qiao X. , Sil A. , Sangtarash S. , Smith S. M. , Wu C. , Robertson C. M. , Nichols R. J. , Higgins S. J. , Sadeghi H. , Vezzoli A.
Published: March 2024

Existing modelling tools, developed to aid the design of efficient molecular wires and to better understand their charge‐transport behaviour and mechanism, have limitations in accuracy and computational cost. Further research is required to develop faster and more precise methods that can yield information on how charge transport properties are impacted by changes in the chemical structure of a molecular wire. In this study, we report a clear semilogarithmic correlation between charge transport efficiency and nuclear magnetic resonance chemical shifts in multiple series of molecular wires, also accounting for the presence of chemical substituents. The NMR data was used to inform a simple tight‐binding model that accurately captures the experimental single‐molecule conductance values, especially useful in this case as more sophisticated density functional theory calculations fail due to inherent limitations. Our study demonstrates the potential of NMR spectroscopy as a valuable tool for characterising, rationalising, and gaining additional insights on the charge transport properties of single‐molecule junctions.
Kinetics of microwave carbothermal reduction of Sb2O3: Isothermal and non‐isothermal microwave thermogravimetric analysis
Authors: Yang Qinsheng , Liu Chenhui , Zhu Xiongjin , Srinivasakannan Chandrasekhar , Li Yingwei , Dai Ying
Published: March 2024

Kinetics of antimony production via carbothermal reduction of Sb2O3–carbon powder–NaCl mixture using microwave and conventional heating was investigated to identify the dominant controlling mechanism. Results of conventional heating revealed the temperature range of conventional carbothermal reduction reaction is 500°C to 800°C, with the average activation energy of each stage being 81.97 kJ/mol (α = 0.1–0.5), 65.17 kJ/mol (α = 0.5–0.75), and 69.86 kJ/mol (α = 0.75–1.0), respectively. In the microwave field, the carbothermal reduction reaction of raw materials can be completed at 600°C to obtain antimony, and the weight loss data of the carbothermal reduction process were recorded for the first time. The above results show that the microwave field enhanced the interfacial chemical effect, accelerated the interfacial diffusion from the metal phase to the oxide phase, and reduced the activation energy of the carbon thermal reduction process to 6.85 kJ/mol. The growth index of antimony grain growth process is estimated to be 4.33, controlled by the surface diffusion. These data provide a reliable theoretical basis for studying the reduction reactions of minerals in microwave fields.
Novel polyurethane foam with low released heat for application in bone binder
Authors: Jiao Gangwei , Cao Yang , Liu Xiaodong , Fu Qiang , Gu Ning , Ren Ying , Sun Youyi
Published: March 2024

Because of the significant advantages of bone adhesives compared with traditional mechanical fixation, many scholars have studied polyurethane bone adhesives. However, polyurethane will release a lot of heat in the reaction process, producing high temperature. The high temperature does not only easily cause a human discomfort but also will destroy the tissue structure of human. In this paper, a new polyurethane composite based on phase transition materials and hydroxyapatite is prepared to reduce released heat for application in bone binder. The mechanical properties, adhesive strength, and released heat‐induced temperature of polyurethane composite are investigated in detail. It exhibits good viscoelastic performance with a large elastic deformation (>30%) and good adhesive strength (>0.2 MPa). Furthermore, the released heat of polyurethane composite is effectively reduced, in which the temperature drastically decreases from 110.4 to 41.8°C. The work does not only confirm formation of high‐performance bone binder but also provides a new method to reduce released heat of polyurethane for various applications.
Tarsals from the Sima de los Huesos Middle Pleistocene site (Atapuerca, Burgos, Spain)
Authors: Pablos Adrián , Arsuaga Juan Luis
Published: March 2024

Here, we provide a complete, updated, and illustrated inventory, as well as a comprehensive study, of the tarsals (rearfoot) recovered from the Middle Pleistocene site of Sima de los Huesos (SH, Atapuerca, Spain) in comparison to other Homo comparative samples, both extant and fossil. The minimum number of individuals (MNI) estimated from the tarsals has been established as 15, which represents 51.7% of the 29 dental individuals identified within the SH sample. Within the SH hominin foot sample, an exclusive combination of primitive or plesiomorphic and derived or autapomorphic traits can be observed when compared with other Homo individuals/populations. Other characters are shared among SH hominins and Neandertals that might represent shared derived or autapomorphic traits for this evolutionary line, and most are likely related to robusticity (e.g., rectangular‐like trochlea of the talus, broad calcanei, broad naviculars, and short lateral cuneiforms). Additionally, we observed some exclusive autapomorphic traits in the SH tarsal sample (e.g., narrow head of the talus and short intermediate cuneiforms). A few exclusive traits in SH tarsal remains are even more robust than in Neandertals (e.g., broad lateral malleolar facet in talus, more projected sustentaculum tali, and broad medial cuneiform). These traits could suggest a slightly higher level of gracilization in the tarsal bones of Neandertals compared to the SH sample that is also supported by other anatomical postcranial skeleton elements. Additionally, some paleobiological inferences are made in relation to body size (stature and body mass) and some associations are proposed within the SH sample. In conclusion, the morphology of the SH tarsi confirms an evolutionary relationship of sister groups between this population and Neandertals, probably representing a morphotype similar to the Neandertal ancestors.
N1‐Benzoylated 5‐(4‐pyridinyl)indazole‐based kinase inhibitors: Attaining haspin and Clk4 selectivity via modulation of the benzoyl substituents
Authors: Aboelfotouh Habiba G. , Abdallah Mennatallah , Khalifa Hend , Aboushady Youssef , Abadi Ashraf H. , Engel Matthias , Abdel‐Halim Mohammad
Published: March 2024

Haspin and Clk4 are both understudied protein kinases (PKs), offering potential targets for the development of new anticancer agents. Thus, the identification of new inhibitors targeting these PKs is of high interest. However, the inhibitors targeting haspin or Clk4 developed to date show a poor selectivity profile over other closely related PKs, increasing the risk of side effects. Herein, we present two newly developed N1‐benzyolated 5‐(4‐pyridinyl)indazole‐based inhibitors (18 and 19), derived from a newly identified indazole hit. These inhibitors exhibit an exceptional inhibitory profile toward haspin and/or Clk4. Compound 18 (2‐acetyl benzoyl) showed a preference to inhibit Clk4 and haspin over a panel of closely related kinases, with sixfold selectivity for Clk4 (IC50 = 0.088 and 0.542 μM, respectively). Compound 19 (4‐acetyl benzoyl) showed high selectivity against haspin over the common off‐target kinases (Dyrks and Clks) with an IC50 of 0.155 μM for haspin. Molecular docking studies explained the remarkable selectivity of 18 and 19, elucidating how the new scaffold can be modified to toggle between inhibition of haspin or Clk4, despite the high homology of the ATP‐binding sites. Their distinguished profile allows these compounds to be marked as interesting chemical probes to assess the selective inhibition of haspin and/or Clk4.
Early executive functioning predicts externalizing problems in neurodiverse preschoolers
Authors: All Katherine , Chawarska Katarzyna , Macari Suzanne L.
Published: March 2024

Children with autism spectrum disorder (ASD) often exhibit externalizing problems, which have been linked with increased anxiety and depression, peer rejection, and parental stress. Identification of early predictors of externalizing behaviors in autism will facilitate identification of vulnerable children and implementation of early preventative interventions. There is ample evidence that executive functioning, social functioning, and temperament are predictive of later externalizing problems in general populations, but less is known about these relations in ASD and other neurodiverse populations, particularly in the early preschool years. To address this gap, we assessed the relations between executive functioning, social functioning, and temperament at age 3 and externalizing problems at age 5 in a sample of neurodiverse children with ASD and other neurodevelopmental disorders and delays. Analyses revealed that severity of early executive functioning impairment predicted increased externalizing problems. Severity of social autism symptoms moderated this relationship such that the effect of executive functioning on externalizing problems decreased as autism symptoms increased. These findings suggest that executive functioning is an important target for identifying and developing interventions for vulnerable children and underscore the necessity of considering severity of autism symptoms when researching the development of externalizing problems in children with neurodevelopmental disorders.
Computer‐aided design to enhance the stability of aldo‐keto reductase KdAKR
Authors: Dai Chen , Tian Jia‐Xin , Chen Yu‐Feng , Ni Yue‐Han , Cui Lei , Cao Hai‐Xing , Song Lin‐Lin , Xu Shen‐Yuan , Wang Ya‐Jun , Zheng Yu‐Guo
Published: March 2024

The aldo‐keto reductase (AKR) KdAKR from Kluyvermyces dobzhanskii can reduce t‐butyl 6‐chloro‐(5S)‐hydroxy‐3‐oxohexanoate ((5S)‐CHOH) to t‐butyl 6‐chloro‐(3R,5S)‐dihydroxyhexanoate ((3R,5S)‐CDHH), which is the key chiral intermediate of rosuvastatin. Herein, a computer‐aided design that combined the use of PROSS platform and consensus design was employed to improve the stability of a previously constructed mutant KdAKRM6. Experimental verification revealed that S196C, T232A, V264I and V45L produced improved thermostability and activity. The “best” mutant KdAKRM10 (KdAKRM6‐S196C/T232A/V264I/V45L) was constructed by combining the four beneficial mutations, which displayed enhanced thermostability. Its T5015 and Tm values were increased by 10.2 and 10.0°C, respectively, and half‐life (t1/2) at 40°C was increased by 17.6 h. Additionally, KdAKRM10 demonstrated improved resistance to organic solvents compared to that of KdAKRM6. Structural analysis revealed that the increased number of hydrogen bonds and stabilized hydrophobic core contributed to the rigidity of KdAKRM10, thus improving its stability. The results validated the feasibility of the computer‐aided design strategy in improving the stability of AKRs.
Renewable energy use, slack financial resources, and board attributes: Does energy efficiency policy matter?
Authors: Uyar Ali , Gerged Ali Meftah , Kuzey Cemil , Karaman Abdullah S.
Published: March 2024

This study examined the impact of slack financial resources, board characteristics (such as gender diversity, tenure, and skill/expertise), and energy efficiency policies on firms' consumption of renewable energy. Using a dataset of 17,753 observations from 2002 to 2019, we primarily utilized fixed‐effects regression, among other methods, for robustness analysis. We find that while slack financial resources, board gender diversity, and energy efficiency policies are positively associated with more renewable energy consumption, board skill is negatively associated with it. Interaction effects showed that firms with more female and tenured directors effectively utilize slack financial resources for increased renewable energy consumption, unlike firms with more expert directors. Energy efficiency policies enhanced the positive impact of female directors on renewable energy consumption but mitigated the influence of expert directors, weakening their association.
Host cell proteins in monoclonal antibody processing: Control, detection, and removal
Authors: Ito Takao , Lutz Herb , Tan Lihan , Wang Bin , Tan Janice , Patel Masum , Chen Lance , Tsunakawa Yuki , Park Byunghyun , Banerjee Subhasis
Published: March 2024

Host cell proteins (HCPs) are process‐related impurities in a therapeutic protein expressed using cell culture technology. This review presents biopharmaceutical industry trends in terms of both HCPs in the bioprocessing of monoclonal antibodies (mAbs) and the capabilities for HCP clearance by downstream unit operations. A comprehensive assessment of currently implemented and emerging technologies in the manufacturing processes with extensive references was performed. Meta‐analyses of published downstream data were conducted to identify trends. Improved analytical methods and understanding of “high‐risk” HCPs lead to more robust manufacturing processes and higher‐quality therapeutics. The trend of higher cell density cultures leads to both higher mAb expression and higher HCP levels. However, HCP levels can be significantly reduced with improvements in operations, resulting in similar concentrations of approx. 10 ppm HCPs. There are no differences in the performance of HCP clearance between recent enhanced downstream operations and traditional batch processing. This review includes best practices for developing improved processes.
When will we have a clone? An industry perspective on the typical CLD timeline
Authors: Clarke Howard , Mayer‐Bartschmid Anke , Zheng Chenxing , Masterjohn Elizabeth , Patel Falguni , Moffat Mark , Wei Qingxiang , Liu Ren , Emmins Robyn , Fischer Simon , Rieder Stephanie , Kelly Thomas
Published: March 2024

Cell line development (CLD) represents a complex but highly critical process during the development of a biological drug. To shed light on this crucial workflow, a team of BioPhorum members (authors) has developed and executed surveys focused on the activities and effort involved in a typical CLD campaign. An average of 27 members from different companies that participate in the BioPhorum CLD working group answered surveys covering three distinguishable stages of a standard CLD process: (1) Pre‐transfection, including vector design and construction; (2) Transfection, spanning the initial introduction of vector into cells and subsequent selection and analysis of the pools; and (3) Single Cell Cloning and Lead Clone Selection, comprising methods of isolating single cells and confirming clonal origin, subsequent expansion and screening processes, and methods for identifying and banking lead clones. The surveys were very extensive, including a total of 341 questions split between antibody and complex molecule CLD processes. In this survey review, the authors interpret and highlight responses for antibody development and, where relevant, contrast complex molecule development challenges to provide a comprehensive industry perspective on the typical time and effort required to develop a CHO production cell line.
Myofascial junction: Emerging insights into the connection between deep/muscular fascia and muscle
Authors: Pirri Carmelo , Petrelli Lucia , Guidolin Diego , Porzionato Andrea , Fede Caterina , Macchi Veronica , De Caro Raffaele , Stecco Carla
Published: March 2024

Muscles and fasciae are mutually connected and are influenced by force transmission. However, the anatomical connectivity and histological features of these structures remain unclear. The aim of this study was to assess the evidence for connection between muscles and deep/muscular fasciae. We assessed this relationship in different topographical regions of human cadavers and in mice. The results showed that myofascial junctions (MFJ) were made up of collagen I immune‐positive structures occupying an average area of 5.11 ± 0.81 μm2, distributed in discrete regions at the interface between muscle and fascia with an average density of 9.7 ± 2.51 MFJ/mm and an average inclination angle of 35.25 ± 1.52°. These specialized structures also showed collagen III and HA immunopositivity and the presence of elastic fibers. The human myofascial junction can be visualized, opening emerging insights into the connection between deep/muscular fascia and muscle.
Helping college students with autism spectrum disorder: Exploring factors affecting use of counselling
Authors: Noble Nicole , Bueno Nicholas , Zatopek Audrey , Hernandez Jeremias
Published: March 2024

Introduction

Individuals with autism spectrum disorder (ASD) experience mental health concerns at a higher prevalence rate than the general population, yet mental health professionals have limited education, training and experience in counselling individuals with ASD.

Methods

To better understand the unique mental health concerns this population encounters, this qualitative study explored the experiences of 102 college students with ASD as they considered, attended and stopped counselling.

Results

Specifically, this study investigated the motives the participants reported for attending counselling, the reasons professionals indicated that the participants should attend counselling, the barriers the participants were confronted with in seeking counselling and the causes for terminating counselling.

Conclusion

Based on these findings, implications for counselling this population and future research are provided.
Investigating the Effects and Mechanisms of Cyclomorusin on Osteoclasts in a High Glucose Environment
Authors: Guo Dong‐Gui , Zhu Jun , Wang Hui‐Juan , Pan Bo‐Wen
Published: March 2024

Diabetes mellitus is an endocrine disease characterized by prolonged hyperglycemia. Prolonged high blood sugar levels interfere with the differentiation and maturation process of OBs and OCs, leading to the onset of osteoporosis. However, OCs differentiation and maturation is a complex regulatory process. In this study, we used a co‐culture system of RAW264.7 and MC3T3‐E1 cells under HG concentration to explore the effect of CYM on OCs in a HG environment. The effects of CYM on the formation and function of OCs were observed using TRAP‐positive cell counts and bone resorption pits. Then, mRNA and protein expression levels of OCs‐related genes were detected by real‐time qPCR and western blotting. The results showed that CYM had an inhibitory effect on OCs differentiation and bone resorption, reduced mRNAs expression of OCs‐associated genes, and downregulated RANKL/RANK/TRAF6 pathway that mediates OCs differentiation. CYM could be a promising natural compound against diabetic osteoporosis.
Synthesis, Theoretical Study, and Anticonvulsant Evaluation of N‐Arylenaminones
Authors: Jiménez‐Vázquez Hugo A. , Guevara‐Salazar J. Alberto , Quintana‐Zavala Delia
Published: March 2024

N‐Arylenaminones are highly versatile compounds which can be synthesized in relatively simple ways. In this work we explored the synthesis of the four monosubstituted N‐(4‐R‐phenyl)enaminones 3 a (R=NO2), 3 b (R=F), 3 c (R=H), and 3 d (R=OMe) with the goal of determining the influence of the substituents′ electronic effects on tautomer stability and biological activity. These compounds were analyzed by means of Density Functional Theory calculations (DFT), to evaluate the relative stability of the possible tautomers. We found that the enaminone structure is the most stable with respect to the ketoimine and iminoenol forms. In addition, all four compounds display anticonvulsant activity, with 3 d being the one that mostly increased latency and mostly decreased the number of convulsions with respect to the control group. The suggested mechanism of action involves blockage of the voltage‐dependent Na+ channels, considering that these molecules meet the structural characteristics needed to block the receptor, as is the case of the positive control molecules phenytoin (PHT) and valproic acid (VPA).
Novel Triazole‐Containing “Dipeptides”: Synthesis, Molecular Docking and Analgesic Activity Studies
Authors: Ghochikyan Tariel V. , Zhamharyan Arusyak G. , Afrikyan Shushanik G. , Frangyan Vardges R. , Galstyan Armen S.
Published: March 2024

Dipeptides of a new structure based on β‐triazolalanines and (L)‐α‐amino acids were synthesized and optimal conditions were developed that ensure both chemical and optical purity of the final products. Molecular docking was carried out and possible intermolecular interactions of dipeptides with potential targets were established. Based on these studies, the analgesic property of chosen dipeptides was studied and it was found that some compounds possess revealed antinociceptive activity in the tail‐flick test.
Efficient Transferase Engineering for SAM Analog Synthesis from Iodoalkanes
Authors: Schülke Kai H. , Fröse Jana S. , Klein Alina , Garcia‐Borràs Marc , Hammer Stephan C.
Published: March 2024

S‐Adenosyl‐l‐methionine (SAM) is an important cosubstrate in various biochemical processes, including selective methyl transfer reactions. Simple methods for the (re)generation of SAM analogs could expand the chemistry accessible with SAM‐dependent transferases and go beyond methylation reactions. Here we present an efficient enzyme engineering strategy to synthesize different SAM analogs from “off‐the‐shelf” iodoalkanes through enzymatic alkylation of S‐adenosyl‐l‐homocysteine (SAH). This was achieved by mutating multiple hydrophobic and structurally dynamic amino acids simultaneously. Combinatorial mutagenesis was guided by the natural amino acid diversity and generated a highly functional mutant library. This approach increased the speed as well as the scale of enzyme engineering by providing a panel of optimized enzymes with orders of magnitude higher activities for multiple substrates in just one round of enzyme engineering. The optimized enzymes exhibit catalytic efficiencies up to 31 M−1 s−1, convert various iodoalkanes, including substrates bearing cyclopropyl or aromatic moieties, and catalyze S‐alkylation of SAH with very high stereoselectivities (>99 % de). We further report a high throughput chromatographic screening system for reliable and rapid SAM analog analysis. We believe that the methods and enzymes described herein will further advance the field of selective biocatalytic alkylation chemistry by enabling SAM analog regeneration with “off‐the‐shelf” reagents.
Porphyrin−BODIPY Dyad: Enhancing Photodynamic Inactivation via Antenna Effect
Authors: Pérez María E. , Durantini Javier E. , Martínez Sol R. , Durantini Andrés M. , Milanesio María E. , Durantini Edgardo N.
Published: March 2024

A porphyrin−BODIPY dyad (P−BDP) was obtained through covalent bonding, featuring a two‐segment design comprising a light‐harvesting antenna system connected to an energy acceptor unit. The absorption spectrum of P−BDP resulted from an overlap of the individual spectra of its constituent parts, with the fluorescence emission of the BODIPY unit experiencing significant quenching (96 %) due to the presence of the porphyrin unit. Spectroscopic, computational, and redox investigations revealed a competition between photoinduced energy and electron transfer processes. The dyad demonstrated the capability to sensitize both singlet molecular oxygen and superoxide radical anions. Additionally, P−BDP effectively induced the photooxidation of L‐tryptophan. In suspensions of Staphylococcus aureus cells, the dyad led to a reduction of over 3.5 log (99.99 %) in cell survival following 30 min of irradiation with green light. Photodynamic inactivation caused by P−BDP was also extended to the individual bacterium level, focusing on bacterial cells adhered to a surface. This dyad successfully achieved the total elimination of the bacteria upon 20 min of irradiation. Therefore, P−BDP presents an interesting photosensitizing structure that takes advantage of the light‐harvesting antenna properties of the BODIPY unit combined with porphyrin, offering potential to enhance photoinactivation of bacteria.
Gastric sarcoidosis diagnosed with endoscopic ultrasound
Authors: El Sharu Husam , Ibarra Stephanie , Chaudhary Ammad , Hidri Sinda , Khan Zarak , Hoo‐Fatt Danielle
Published: March 2024

Key Clinical Message

Endoscopic ultrasonography (EUS) is crucial in diagnosing gastrointestinal sarcoidosis, especially when patients exhibit refractory abdominal symptoms. Our case highlights the significance of considering sarcoidosis in such cases and emphasizes the utility of EUS for accurate diagnosis and guiding appropriate treatment.

Gastrointestinal sarcoidosis is a rare and challenging manifestation of sarcoidosis that often presents with nonspecific abdominal symptoms, making diagnosis a complex process. We report the case of a 46‐year‐old African American female who experienced chronic epigastric abdominal pain, recurrent nausea, vomiting, and diarrhea for 15 years. Despite extensive investigations, including multiple biopsies, she was misdiagnosed with cyclic vomiting syndrome. Subsequently, an endoscopic ultrasound (EUS) revealed prominent lymph nodes and gastric granulomas, leading to a diagnosis of GS. This case underscores the importance of considering sarcoidosis in patients with refractory abdominal symptoms and highlights the utility of EUS in diagnosing this rare condition.
Manipulating photogenerated electron flow in nickel single‐atom catalysts for photocatalytic CO2 reduction into tunable syngas
Authors: Zhang Yida , Wang Qingyu , Wu Lihui , Pan Haibin , Liu Chengyuan , Lin Yue , Wang Gongming , Zheng Xusheng
Published: March 2024

The key to designing photocatalysts is to orient the migration of photogenerated electrons to the target active sites rather than dissipate at inert sites. Herein, we demonstrate that the doping of phosphorus (P) significantly enriches photogenerated electrons at Ni active sites and enhances the performance for CO2 reduction into syngas. During photocatalytic CO2 reduction, Ni single‐atom‐anchored P‐modulated carbon nitride showed an impressive syngas yield rate of 85 μmol gcat−1 h−1 and continuously adjustable CO/H2 ratios ranging from 5:1 to 1:2, which exceeded those of most of the reported carbon nitride‐based single‐atom catalysts. Mechanistic studies reveal that P doping improves the conductivity of catalysts, which promotes photogenerated electron transfer to the Ni active sites rather than dissipate randomly at low‐activity nonmetallic sites, facilitating the CO2‐to‐syngas photoreduction process.
Suppressing Cis/Trans ‘Ring‐Flipping’ in Organoaluminium(III)‐2‐Pyridyl Dimers–Design Strategies Towards Lewis Acid Catalysts for Alkene Oligomerisation
Authors: Choudhury Dipanjana , Lam Ching Ching , Farag Nadia L. , Slaughter Jonathan , Bond Andrew D. , Goodman Jonathan M. , Wright Dominic S.
Published: March 2024

Owing to its high natural abundance compared to the commonly used transition (precious) metals, as well as its high Lewis acidity and ability to change oxidation state, aluminium has recently been explored as the basis for a range of single‐site catalysts. This paper aims to establish the ground rules for the development of a new type of cationic alkene oligomerisation catalyst containing two Al(III) ions, with the potential to act co‐operatively in stereoselective assembly. Five new dimers of the type [R2Al(2‐py′)]2 (R=Me, iBu; py′=substituted pyridyl group) with different substituents on the Al atoms and pyridyl rings have been synthesised. The formation of the undesired cis isomers can be suppressed by the presence of substituents on the 6‐position of the pyridyl ring due to steric congestion, with DFT calculations showing that the selection of the trans isomer is thermodynamically controlled. Calculations show that demethylation of the dimers [Me2Al(2‐py′)]2 with Ph3C+ to the cations [{MeAl(2‐py’)}2(μ‐Me)]+ is highly favourable and that the desired trans disposition of the 2‐pyridyl ring units is influenced by steric effects. Preliminary experimental studies confirm that demethylation of [Me2Al(6‐MeO‐2‐py)]2 can be achieved using [Ph3C][B(C6F5)4].
Controlling the Crystal Growth of DNA Molecules via Strategic Chemical Modifications
Authors: Lyu Jiazhen , Zhu Tingyu , Zhou Yan , Zhao Ting , Fei Meiling , Zhong Xiaowu , He Hongfei
Published: March 2024

Intermolecular interactions are critical to the crystallization of biomolecules, yet the precise control of biomolecular crystal growth based on these interactions remains elusive. To understand the connections between the crystallization kinetics and the strength of intermolecular interactions, herein we have employed DNA triangular crystals and modified ones as a versatile tool to investigate how the strength of intermolecular interaction affects crystal growth. Interestingly, we have found that the 2’‐O‐methylation at sticky ends of the DNA triangle could strengthen its intermolecular interaction, resulting in the accelerated formation of smaller crystals. Conversely, phosphorothioate modification could weaken the sticky‐end cohesion and delay the nucleation, resulting in formation of fewer but larger crystals. In addition, these modification effects were consistently observed in the crystallization of a DNA decamer. In one word, our experimental results demonstrate that the strength of intermolecular interaction directly impacts crystal growth. It suggests that 2’‐O‐methylation and phosphorothioate modification represents a rational strategy for controlling DNA molecules grow into desired crystals and it also facilitates structural determination.
Injectable Chitosan Hydrogels Doped with 2D Peptide Nanosheet‐Drug Conjugates for Glutathione‐Responsive Sustained Drug Delivery
Authors: Luan Xin , Hu Huiqiang , Zhu Danzhu , He Peng , Sun Zhengang , Xi Yongming , Wei Gang
Published: March 2024

The development of novel and effective drug delivery systems aimed at enhancing therapeutic profile and efficacy of therapeutic agents is a critical challenge in modern medicine. This study presents an intelligent drug delivery system based on self‐assembled two‐dimensional peptide nanosheets (2D PNSs). Leveraging the tunable properties of amino acid structures and sequences, we design a peptide with the sequence of Fmoc‐FKKGSHC, which self‐assembles into 2D PNSs with uniform structure, high biocompatibility, and excellent degradability. Covalent attachment of thiol‐modified doxorubicin (DOX) drugs to 2D PNSs via disulfide bond results in the peptide‐drug conjugates (PDCs), which is denoted as PNS‐SS‐DOX. Subsequently, the PDCs are encapsulated within the injectable, thermosensitive chitosan (CS) hydrogels for drug delivery. The designed drug delivery system demonstrates outstanding pH‐responsiveness and sustained drug release capabilities, which are facilitated by the characteristics of the CS hydrogels. Meanwhile, the covalently linked disulfide bond within the PNS‐SS‐DOX is responsive to intracellular glutathione (GSH) within tumor cells, enabling controlled drug release and significantly inhibiting the cancer cell growth. This responsive peptide‐drug conjugate based on a 2D peptide nanoplatform paves the way for the development of smart drug delivery systems and has bright prospects in the future biomedicine field.