bluuebunny/crossref_metadata_2025 huggingface dataset:
Indomethacin and 20‐hydroxyecdysone influence protein expression in a Spodoptera frugiperda nervous system cell line
Authors: Wang Yong , Buer Benjamin , Goodman Cynthia L. , Kang David , Reall Tamra , Dohn Susanne , Ringbauer Joseph , Li Yaofa , Geibel Sven , Stanley David
Published: February 2024

Insecticide mode of action studies provide insights into how new insecticidal actives function and contribute to assessing safety to humans and nontarget organisms. Insect cell lines that express potential target sites can serve as valuable tools in this effort. In this paper, we report on the influence of two signaling molecules on protein expression in a nervous system cell line established from Spodoptera frugiperda (Bayer/BCIRL‐SfNS2‐0714‐TR). We selected this line because we established it in our laboratory and we are experienced in using it. Cells were exposed to the insect developmental hormone (1 µg/mL 20‐hydroxyecdysone, 20E) and/or a cyclooxygenase (COX) inhibitor (25 μM indomethacin, INDO; inhibits prostaglandin [PG] biosynthesis) for 24 h (Day 2), 72 h (Day 4), or 120 h (Day 6). We selected a PG biosynthesis inhibitor because PGs act in many aspects of insect biology, such as embryonic development, immunity, and protein phosphorylation. We selected the developmental hormone, 20E, because it also acts in fundamental aspects of insect biology. We identified specific proteins via in silico analysis. Changes in protein expression levels were determined using liquid chromatography‐mass spectrometry (MS) + MS‐MS. The largest number of changes in protein expression occurred on Day 2. The combination of 20E plus INDO led to 222 differentially expressed proteins, which documents the deep significance of PGs and 20E in insect biology. 20E and, separately, INDO led to changes in 30 proteins each (p value < 0.01; >2X or <0.5X‐fold changes). We recorded changes in the expression of 9 or 12 proteins (20E), 10 or 6 proteins (INDO), and 21 or 20 proteins (20E + INDO) on D4 and D6, respectively. While the cell line was established from neuronal tissue, the differentially expressed proteins act in a variety of fundamental cell processes. In this paper, we moved beyond a list of proteins by providing detailed, Gene Ontology term analyses and enrichment, which offers an in‐depth understanding of the influence of these treatments on the SfNS2 cells. Because proteins are active components of cell physiology in their roles as enzymes, receptors, elements of signaling transduction pathways, and cellular structures, changes in their expression levels under the influence of signaling molecules provide insights into their function in insect cell physiology.
BmPGPR‐L4 is a negative regulator of the humoral immune response in the silkworm Bombyx mori
Authors: Yang Weiyi , Lin Yongyi , He Yanying , Li Qi , Chen Weijian , Lin Qingsha , Swevers Luc , Liu Jisheng
Published: February 2024

Toll, immune deficiency and prophenoloxidase cascade represent vital immune signaling pathways in insects. Peptidoglycan recognition proteins (PGRPs) are innate immune receptors that activate and regulate the immune signaling pathways. Previously, we reported that BmPGPR‐L4 was induced in the silkworm Bombyx mori larvae by bacteria and peptidoglycan challenges. Here, we focused on the function of BmPGRP‐L4 in regulating the expression of antimicrobial peptides (AMPs). The hemolymph from BmPGRP‐L4‐silenced larvae exhibited an enhanced inhibitory effect on the growth of Escherichia coli, either by growth curve or inhibitory zone experiments. Coincidentally, most of the AMP genes were upregulated after RNAi of BmPGRP‐L4. Oral administration of heat‐inactivated E. coli and Staphylococcus aureus after RNAi of BmPGRP‐L4 resulted in the increased expression of BmPGRP‐L4 in different tissues of the silkworm larvae, revealing an auto‐regulatory mechanism. By contrast, the expression of most AMP genes was downregulated by oral bacterial administration after RNAi of BmPGRP‐L4. The above results demonstrate that BmPGRP‐L4 recognizes bacterial pathogen‐associated molecular patterns and negatively regulates AMP expression to achieve immunological homeostasis. As a negative regulator, BmPGPR‐L4 is proposed to be involved in the feedback regulation of the immune signaling pathways of the silkworm to prevent excessive activation of the immune response.
Hyperuricemia Subtypes Classified According to Renal Uric Acid Handling Manifesting Distinct Phenotypic and Genetic Profiles in People With Gout
Authors: Qi Han , Sun Mingshu , Terkeltaub Robert , Merriman Tony R. , Chen Haibing , Li Zhiqiang , Ji Aichang , Xue Xiaomei , Sun Wenyan , Wang Can , Li Xinde , He Yuwei , Cui Lingling , Dalbeth Nicola , Li Changgui
Published: February 2024

Objective

Hyperuricemia can be stratified into four subtypes according to renal uric acid handling. The aim of this study was to comprehensively describe the biologic characteristics (including genetic background) of clinically defined hyperuricemia subtypes in two large geographically independent gout cohorts.

Methods

Hyperuricemia subtype was defined as renal uric acid overload (ROL), renal uric acid underexcretion (RUE), combined, or renal normal. Twenty single nucleotide polymorphisms (SNPs) previously identified as gout risk loci or associated with serum urate (SU) concentration in the East Asian population were genotyped. Weighted polygenic risk scores were calculated to assess the cumulative effect of genetic risks on the subtypes.

Results

Of the 4,873 participants, 8.8% had an ROL subtype, 60.9% RUE subtype, 23.1% combined subtype, and 7.2% normal subtype. The ROL subtype was independently associated with older age at onset, lower SU, tophi, and diabetes mellitus; RUE was associated with lower body mass index (BMI) and non–diabetes mellitus; the combined subtype was associated with younger age at onset, higher BMI, SU, estimated glomerular filtration rate (eGFR), and smoking; and the normal subtype was independently associated with older age at onset, lower SU, and eGFR. Thirteen SNPs were associated with gout with 6 shared loci and subtype‐dependent risk loci patterns. High polygenic risk scores were associated with ROL subtype (odds ratio [OR] = 9.63, 95% confidence interval [95% CI] 4.53–15.12), RUE subtype (OR = 2.18, 95% CI 1.57–3.03), and combined subtype (OR = 6.32, 95% CI 4.22–9.48) compared with low polygenic risk scores.

Conclusion

Hyperuricemia subtypes classified according to renal uric acid handling have subtype‐specific clinical and genetic features, suggesting subtype‐unique pathophysiologic mechanisms.
Faith and facts: Exploring the intersection of religion and science among anatomy educators
Authors: Brooks William S. , Deweese Joseph E. , Wilson Adam B.
Published: February 2024

The intersection of religion and science often elicits polarizing views among scientists, though approximately half of American scientists identify as religious. Mounting evidence also supports the role of spirituality in comprehensive patient care. The purpose of this study was to explore the religiosity of faculty who teach in the anatomical sciences at U.S. colleges and universities. Surveys were administered to anatomists through two professional societies. Two‐thirds (64.9%, 74/114) of respondents identified as religious, 26.3% (30/114) as atheist, and 8.8% (10/114) as agnostic. Most respondents (64.9%, 74/114) disagreed with the statement, “There is no place for religion and science to intersect.” Approximately one in three respondents expressed concern that sharing/disclosing their religious beliefs would negatively affect the perceptions of colleagues (32.5%, 37/114) and students (28.9%, 33/114) toward them. Faculty at faith‐based institutions were more open to disclosing their beliefs (p = 0.045), and highly religious individuals were more concerned (p = 0.001). Fewer than one‐fifth of respondents 17.5% (20/114) personally experienced mistreatment or discrimination within academic settings due to their religious beliefs. Most respondents held politically liberal‐leaning views (71.0%, 76/107). Highly religious individuals were more likely to be politically conservative (p < 0.001). Overall, this study demonstrates that the number of anatomists who identify as religious may be higher than that of other biological disciplines and that mistreatment due to religious views remains a challenge for some in the profession. Continued dialogue regarding the role of religion in professional identity expression may be an important step in mitigating religion‐focused mistreatment and discrimination in academic settings.
Pd‐Catalyzed Oxidative C−H Arylation of (Poly)fluoroarenes with Aryl Pinacol Boronates and Experimental and Theoretical Studies of its Reaction Mechanism
Authors: Budiman Yudha P. , Putra Miftahussurur Hamidi , Ramadhan Muhammad R. , Hannifah Raiza , Luz Christian , Ghafara Ilham Z. , Rustaman Rustaman , Ernawati Engela E. , Mayanti Tri , Groß Axel , Radius Udo , Marder Todd B.
Published: February 2024

We report the synergistic combination of Pd(OAc)2 and Ag2O for the oxidative C−H arylation of (poly)fluoroarenes with aryl pinacol boronates (Ar‐Bpin) in DMF as the solvent. This procedure can be conducted easily in air, and without using additional ligands, to afford the fluorinated unsymmetrical biaryl products in up to 98 % yield. Experimental studies suggest that the formation of [PdL2(C6F5)2] in DMF as coordinating solvent does not take place under the reaction conditions as it is stable to reductive elimination and thus would deactivate the catalyst. Thus, the intermediate [Pd(DMF)2(ArF)(Ar)] must be formed selectively to give desired arylation products. DFT calculations predict a low barrier (5.87 kcal/mol) for the concerted metalation deprotonation (CMD) process between C6F5H and the Pd(II) species formed after transmetalation between the Pd(II)X2 complex and aryl‐Bpin which forms a Pd‐Arrich species. Thus a Pd(Arrich)(Arpoor) complex is generated selectively which undergoes reductive elimination to generate the unsymmetrical biaryl product.
Controllability, observability, and stability of φ‐conformable fractional linear dynamical systems
Authors: Sadek Lakhlifa
Published: February 2024

This paper focuses on two main aspects. Firstly, we introduce a generalized form of conformable fractional derivatives called
‐conformable fractional derivatives
along with their corresponding integrals
. We also present several theorems related to these derivatives. Secondly, we investigate the observability, controllability, and stability of a fractional dynamical system known as the
‐conformable fractional dynamical system (
‐CF‐DS). We establish the connection between controllability, the controllability matrix, and the fractional
‐conformable fractional differential Lyapunov equation (
‐CF‐DLE). We prove that the
‐CF‐DS is stable if and only if all eigenvalues of the matrix
have negative real parts. Moreover, we provide theorems regarding the observability of an
‐CF‐DS. To demonstrate the efficacy of our results, we include illustrative examples.
Clathrin controls bidirectional communication between T cells and antigen presenting cells
Authors: Kvalvaag Audun , Dustin Michael L.
Published: February 2024

In circulation, T cells are spherical with selectin enriched dynamic microvilli protruding from the surface. Following extravasation, these microvilli serve another role, continuously surveying their environment for antigen in the form of peptide‐MHC (pMHC) expressed on the surface of antigen presenting cells (APCs). Upon recognition of their cognate pMHC, the microvilli are initially stabilized and then flatten into F‐actin dependent microclusters as the T cell spreads over the APC. Within 1–5 min, clathrin is recruited by the ESCRT‐0 component Hrs to mediate release of T cell receptor (TCR) loaded vesicles directly from the plasma membrane by clathrin and ESCRT‐mediated ectocytosis (CEME). After 5‐10 min, Hrs is displaced by the endocytic clathrin adaptor epsin‐1 to induce clathrin‐mediated trans‐endocytosis (CMTE) of TCR‐pMHC conjugates. Here we discuss some of the functional properties of the clathrin machinery which enables it to control these topologically opposite modes of membrane transfer at the immunological synapse, and how this might be regulated during T cell activation.
Proteomic analysis of exosomal proteins associated with bone healing speed in a rat tibial fracture model
Authors: Hong Haifeng , Lin Changhui , Fang Min , Liu Juntian , Hsu Hung‐Chih , Chang Chih‐Jung , Wang Haibing
Published: February 2024

This study investigates the impact of exosomes on bone fracture healing in a rat tibial model, distinguishing between fast and slow healing processes. Bone healing and protein expression were assessed through X‐ray examinations, hematoxylin and eosin staining, and immunohistochemical staining. Exosomes were isolated, characterized and subjected to liquid chromatography–mass spectrometry for protein analysis. Molecular differences were explored using differentially expressed protein analysis, Kyoto Encyclopedia of Genes and Genomes pathway enrichment and protein–protein interaction networks. Differential bone healing patterns and protein expressions were observed between the control and model groups. Exosomes were successfully isolated and characterized, revealing 2004 identified proteins, including distinct expression profiles. Notably, ribosomal proteins, ferritin and beta‐actin emerged as pivotal players in bone fracture healing. This study unveils dynamic changes in bone healing and underscores the role of exosomes in the process. Identified proteins and pathways offer valuable insights for developing innovative therapeutic strategies for bone healing.
Functional neurological signs in hypermobile Ehlers–Danlos syndrome and hypermobile spectrum disorders with suspected neuropathic pain
Authors: Fernandez Aurore , Jaquet Manon , Aubry‐Rozier Bérengère , Suter Marc , Aybek Selma , Berna Chantal
Published: February 2024

Background

The hypermobile Ehlers–Danlos syndrome (hEDS) and hypermobility spectrum disorders (HSD) are connective tissue disorders characterized by generalized joint hypermobility, associated with chronic pain and several symptoms, such as fatigue, dysautonomia, as well as psychiatric co‐morbidities. Clinical observations of unusual manifestations during systematic sensory testing raised the question of a possible co‐existence with a functional neurological disorder (FND). Hence, this study aimed to assess the presence of positive functional neurological signs (FNS) in a cohort of patients with hEDS/HSD.

Methods

The clinical data of hEDS/HSD patients (N = 24) were retrospectively analyzed and compared to a prospectively recruited age‐/sex‐matched healthy control group (N = 22). Four motor‐ and three sensory‐positive FNS were assessed.

Results

Twenty‐two patients (92%) presented at least one motor or sensory FNS. Five patients (21%) presented only a single FNS, 14 presented between 2 and 4 FNS (58%), and 3 patients presented 5 or more FNS (12%). None of the healthy controls presented motor FNS, and only two presented a sensory FNS.

Conclusions

The presence of FNS in hEDS/HSD deserves better clinical detection and formal diagnosis of FND to offer more adequate care in co‐morbid situations. In fact, FND can severely interfere with rehabilitation efforts in hEDS/HSD, and FND‐targeted physical therapy should perhaps be combined with EDS/HSD‐specific approaches.
Effects of finance knowledge influencer qualities on investment willingness and the moderation of followers' risk tolerance
Authors: Luan Chi‐Cheng , Chen Kuo‐Liang , Ko Chi‐Yu , Lin Po‐Min , Phan The Anh
Published: February 2024

Fueled by the rise of social media, internet celebrities (or influencers) are a subgroup of public figures who have gained extreme public attention in recent years. In this study, we examined the qualities of finance knowledge influencers to elucidate the impact that investment discussions or tutorials posted by influencers have on followers' and audiences' investment willingness. We adopted attractiveness, expertise, and trustworthiness as the independent variables, followers' risk tolerance as the moderator, and followers' investment willingness as the dependent variable. For data collection, respondents were instructed to watch three different influencer videos and complete a questionnaire. A total of 327 valid questionnaires were collected and analyzed. The questionnaire survey results showed that influencers' attractiveness expertise, and trustworthiness positively affected followers' investment willingness. Furthermore, followers' risk tolerance negatively moderates the relationship between influencer attractiveness and investment willingness, but it positively moderates the relationship between influencer trustworthiness and investment willingness. The empirical findings of this study theoretically contribute to academics and have practical implications in the real world. We propose several suggestions for future research.
Chemical Profiling and Enzyme Inhibitory Activities of Essential Oil Isolated from Pistacia khinjuk Leaves: Insights On GC‐MS Analysis and Skin Aging‐Relevant Enzymes
Authors: Kamli Hossam , Ali Abd‐Allah M. , Salem Yasmeen H. , Shaikh Ahmad , El‐Nashar Heba A. S.
Published: February 2024

Pistacia khinjuk is a species of flowering plants belonging to family Anacardiaceae, with promising pharmacological activities like antioxidants, anti‐inflammatory, antiviral, and antimicrobial. This study aimed to investigate the GC‐MS chemical composition of essential oil isolated from Pistacia khinjuk leaves and its inhibitory properties against aging‐relevant enzymes such a collagenase and elastase. The isolated oil showed predominance of β‐cadinene (15.34 %), γ‐amorphene (8.50 %), α‐cadinol (8.14 %), τ‐cadinol (7.57 %), (E)‐β‐caryophyllene (5.77 %), α‐pinene (4.70 %), phytol (4.57 %), α‐muurolene (3.30 %), (+)‐epi‐bicyclosesquiphellandrene (3.21 %), and cubenene (3.16 %). Further, it showed remarkable inhibitory activities against collagenase and elastase with IC50 values of 15.61±0.69 and 41.12±2.09 μg/mL, respectively compared to epigallocatechin gallate (IC50=29.52±1.3 μg/mL and 26.86±1.37 μg/mL). as a conclusion, the leaf oil is recommended for topical cosmetic preparations to retard skin aging symptoms such as wrinkles. However, the bioavailability assessment and toxicological profile should be considered in the future studies.
Noncoding RNAs and programmed cell death in hepatocellular carcinoma: Significant role of epigenetic modifications in prognosis, chemoresistance, and tumor recurrence rate
Authors: Arefnezhad Reza , Ashna Sara , Rezaei‐Tazangi Fatemeh , Arfazadeh Seyed Mahdi , Seyedsalehie Seyede Shabnam , Yeganeafrouz Shaghayegh , Aghaei Melika , Sanandaji Mandana , Davoodi Ramin , Abadi Sareh Ranjbar Karim , Vosough Massoud
Published: February 2024

Hepatocellular carcinoma (HCC) is the most common type of liver cancer with a high death rate in the world. The molecular mechanisms related to the pathogenesis of HCC have not been precisely defined so far. Hence, this review aimed to address the potential cross‐talk between noncoding RNAs (ncRNAs) and programmed cell death in HCC. All related papers in the English language up to June 2023 were collected and screened. The searched keywords in scientific databases, including Scopus, PubMed, and Google Scholar, were HCC, ncRNAs, Epigenetic, Programmed cell death, Autophagy, Apoptosis, Ferroptosis, Chemoresistance, Tumor recurrence, Prognosis, and Prediction. According to the reports, ncRNAs, comprising long ncRNAs, microRNAs, circular RNAs, and small nucleolar RNAs can affect cell proliferation, migration, invasion, and metastasis, as well as cell death‐related processes, such as autophagy, ferroptosis, necroptosis, and apoptosis in HCC by regulating cancer‐associated genes and signaling pathways, for example, phosphoinositide 3‐kinase/Akt, extracellular signal‐regulated kinase/MAPK, and Wnt/β‐catenin signaling pathways. It seems that ncRNAs, as epigenetic regulators, can be utilized as biomarkers in diagnosis, prognosis, survival and recurrence rates prediction, chemoresistance, and evaluation of therapeutic response in HCC patients. However, more scientific evidence is suggested to be accomplished to confirm these results.
LncRNA HOTTIP promotes LPS‐induced lung epithelial cell injury by recruiting DNMT1 to epigenetically regulate SP‐C
Authors: Li Shuang , Li Shuangjia , Gao Zhanqun , Liu Yang
Published: February 2024

The objective of this study was to elucidate the involvement of the long noncoding RNA (lncRNA) HOTTIP in acute lung injury and understand the underlying mechanisms. Relevant expression of mRNAs and proteins were assessed by qRT‐PCR and western blot assays. Cell viability was determined by employing the CCK‐8 assay, and apoptosis was quantified through TUNEL staining. The concentration of inflammatory factors was measured by ELISA. The degree of DNA methylation was quantified through MSP assay. The interaction between HOTTIP and DNA methyltransferase 1 (DNMT1) was examined by RIP assay. LPS upregulated HOTTIP, whereas downregulated SP‐C level in AEC II cells. HOTTIP knockdown inhibited LPS‐induced apoptosis and the secretion of inflammatory cytokines (TNF‐α, IL‐1β and IL‐6) in AEC II cells. Mechanistically, HOTTIP recruited DNMT1 to the SP‐C promoter, thereby facilitating DNA methylation of SP‐C and suppressing its expression. Additionally, inhibitory of SP‐C reversed the effects of HOTTIP or DNMT1 knockdown on apoptosis and inflammation in AEC II cells induced by LPS. HOTTIP recruited DNMT1 to epigenetically inhibit SP‐C expression, leading to the promotion of lung epithelial cell injury caused by LPS, suggesting that targeting HOTTIP may be an effective strategy for the therapy of lung epithelial cell injury.
Flame‐assisted ultrafast synthesis of functionalized carbon nanosheets for high‐performance sodium storage
Authors: Chen Chen , Yan Dong , Von Lim Yew , Liu Lei , Li Xue Liang , Chen Junjie , Li Tian Chen , Zhu Youyu , Cai Jiangtao , Huang Ying , Zhang Yating , Yang Hui Ying
Published: February 2024

The unique structural features of hard carbon (HC) make it a promising anode candidate for sodium‐ion batteries (SIB). However, traditional methods of preparing HC require special equipment, long reaction times, and large energy consumption, resulting in low throughputs and efficiency. In our contribution, a novel synthesis method is proposed, involving the formation of HC nanosheets (NS‐CNs) within minutes by creating an anoxic environment through flame combustion and further introducing sulfur and nitrogen sources to achieve heteroatom doping. The effect of heterogeneous element doping on the microstructure of HC is quantitatively analyzed by high‐resolution transmission electron microscopy and image processing technology. Combined with density functional theory calculation, it is verified that the functionalized HC exhibits stronger Na+ adsorption ability, electron gain ability, and Na+ migration ability. As a result, NS‐CNs as SIB anodes provide an ultrahigh reversible capacity of 542.7 mAh g−1 at 0.1 A g−1, and excellent rate performance with a reversible capacity of 236.4 mAh g−1 at 2 A g−1 after 1200 cycles. Furthermore, full cell assembled with NS‐CNs as the can present 230 mAh g−1 at 0.5 A g−1 after 150 cycles. Finally, in/ex situ techniques confirm that the excellent sodium storage properties of NS‐CNs are due to the construction of abundant active sites based on the novel synthesis method for realizing the reversible adsorption of Na+. This work provides a novel strategy to develop novel carbons and gives deep insights for the further investigation of facile preparation methods to develop high‐performance carbon anodes for alkali‐ion batteries.
Design strategies and recent advancements of solid‐state supercapacitor operating in wide temperature range
Authors: Zhou Jie , Zhu Zhengfeng , Shi Wenhui , Shi Xiangyu , Zheng Zhuoyuan , Xiong Ye , Zhu Yusong
Published: February 2024

Solid‐state supercapacitors (SSCs) are emerging as one of the promising energy storage devices due to their high safety, superior power density, and excellent cycling life. However, performance degradation and safety issues under extreme conditions are the main challenges for the practical application. With the expansion of human activities, such as space missions, polar exploration, and so on, the investigation of SSC with wide temperature tolerance, high energy density, power density, and sustainability is highly desired. In this review, the effects of temperature on SSC are systematically illustrated and clarified, including the properties of the electrolyte, ion diffusion, and reaction dynamics of the supercapacitor. Subsequently, we summarize the recent advances in wide‐temperature‐range SSCs from the aspect of electrolyte modification, electrode design, and interface adjustment between electrode and electrolyte, especially with critical concerns on ionic conductivity and cycling stability. In the end, a perspective is presented, expecting to promote the practical application of the SSC in harsh conditions.
A review on ultra‐small undoped MoS2 as advanced catalysts for renewable fuel production
Authors: Liu Guoping , Ding Lingling , Meng Yuxuan , Ali Ahmad , Zuo Guifu , Meng Xianguang , Chang Kun , Li Oi Lun , Ye Jinhua
Published: February 2024

Molybdenum disulfide (MoS2) has garnered significant attention in the field of catalysis due to the high density of active sites in its unique two‐dimensional (2D) structure, which could be developed into numerous high‐performance catalysts. The synthesis of ultra‐small MoS2 particles (<10 nm) is highly desired in various experimental studies. The ultra‐small structure could often lead to a distinct S–Mo coordination state and nonstoichiometric composition in MoSx, minimizing in‐plane active sites of the 2D structure and making it probable to regulate the atomic and electronic structure of its intrinsic active sites on a large extent, especially in MoSx clusters. This article summarizes the recent progress of catalysis over ultra‐small undoped MoS2 particles for renewable fuel production. Through a systematic review of their synthesis, structural, and spectral characteristics, as well as the relationship between their catalytic performance and inherent defects, we aim to provide insights into catalysis over this matrix that may potentially enable advancement in the development of high‐performance MoS2‐based catalysts for sustainable energy generation in the future.
The Role of Base in Reaction Performance of Photochemical Synthesis of Thiazoles: An Integrated Theoretical and Experimental Study
Authors: Xu Jiaxin , Ye Xiaoyu , Lv Zongchao , Chen Yi‐Hung , Wang Xiang Simon
Published: February 2024

Artificial intelligence (AI)/machine learning (ML) is emerging as pivotal in synthetic chemistry, offering revolutionary potential in retrosynthetic analysis, reaction conditions and reaction prediction. We have combined chemical descriptors, primarily based on Density Functional Theory (DFT) calculations, with various AI/ML tools such as Multi‐Layer Perceptron (MLP) and Random Forest (RF), to predict the synthesis of 2‐arylbenzothiazole in photoredox reactions. Significantly, our models underscore the critical role of the molecular structure and physicochemical characteristics of the base, especially the total atomic polarizabilities, in the rate‐determining steps involving cyclohexyl and phenethyl moieties of the substrate. Moreover, we validated our findings in articles through experimental studies. It showcases the power of AI/ML and quantum chemistry in shaping the future of organic chemistry.
A Tandem Hydroformylation‐Organocatalyzed Friedel‐Crafts Reaction for the Synthesis of Diindolylmethanes
Authors: Miller Lukas , Bauer Felix , Breit Bernhard
Published: February 2024

Herein, we present an efficient and atom‐economic tandem hydroformylation organocatalyzed Friedel‐Crafts reaction sequence for the synthesis of diindolylmethanes. Classic syntheses have relied on (Lewis) acid activation of aldehydes, which are often not commercially available and rather sensitive in handling. In contrast, the combination of rhodium‐catalyzed hydroformylation and subsequent organocatalytic activation of the in‐situ formed aldehydes allows the use of readily available and stable alkenes with various functional groups while avoiding acidic conditions to expand the range of available diindolylmethanes. A broad scope of diindolylmethanes was prepared in yields up to 85 % demonstrates the utility of the presented method.
Nanoreactor Confined and Enriched Intermediates for Electroreduction of CO2 to C2+ Products
Authors: Cao Yucheng , Jia Chunmei , Fan Wenjun , Li Jiangnan , Zhang Fuxiang
Published: February 2024

In the process of electroreduction of carbon dioxide (eCO2RR) to multi‐carbon (C2+) products, it is imperative to enhance the concentration of key intermediate species on the catalyst surface. The utilization of micro‐nano reactors to achieve confinement effects has been widely observed in various catalytic reactions, yet it has seldom been employed in eCO2RR. Here, we present a novel nanoreactor composed of stacked CuS nanosheets for eCO2RR to C2+ products. In comparison to catalyst comprising of nanosheet with open space, the C−C coupling within this confined nanospace is significantly enhanced, resulting in the increase of Faraday efficiency (FE) of C2+ products to 53 %. In situ infrared (IR) spectroscopy reveals the confinement and enrichment of key intermediate by the nanoreactor. Our research findings demonstrate that a meticulously designed nanoreactor can elevate the selectivity of C2+ products, thereby aiding in the design of eCO2RR catalysts.
From the Total Synthesis of Semi–Viriditoxin, Semi–Viriditoxic Acid and Dimeric Naphthopyranones to their Biological Activities in Burkitt B Cell Lymphoma
Authors: Weber Frederike , Weber Anja , Schmitt Laura , Lechtenberg Ilka , Greb Julian , Henßen Birgit , Wesselborg Sebastian , Pietruszka Jörg
Published: February 2024

Dimeric naphthopyranones are known to be biologically active, however, for the corresponding monomeric naphthopyranones this information is still elusive. Here the first enantioselective total synthesis of semi‐viriditoxic acid as well as the synthesis of semi–viriditoxin and derivatives is reported. The key intermediate in the synthesis of naphthopyranones is an α,β‐unsaturated δ‐lactone, which we synthesized in two different ways (Ghosez–cyclization and Grubbs ring–closing metathesis), while the domino–Michael–Dieckmann reaction of the α,β‐unsaturated δ‐lactone with an orsellinic acid derivative is the key reaction. A structure‐activity relationship study was performed measuring the cytotoxicity in Burkitt B lymphoma cells (Ramos). The dimeric structure was found to be crucial for biological activity: Only the dimeric naphthopyranones showed cytotoxic and apoptotic activity, whereas the monomers did not display any activity at all.
A New Molybdenum Blue Structure Type: How Uranium Expands this Family of Polyoxometalates
Authors: Felton Daniel E. , Smith Kyson R. , Poole Nicholas A. , Cronberger Karl , Burns Peter C.
Published: February 2024

The assembly of molybdenum polyoxometalates (POMs) has afforded large discrete nanoclusters with varied degrees of reduction such as the ~20 % reduced molybdenum blues. While many heterometals have been incorporated into these clusters to afford new properties, uranium has yet to be reported. Here we report the first uranium containing molybdenum blue clusters and the unique properties exhibited by this incorporation. The uranyl ion (UO22+) directs formation of Mo72U8, a square POM comprised of two faces connected by eight edge‐sharing molybdenum dimers. Mo72U8, a chiral cluster, crystallizes as a racemic mixture and, in the solid state, has a ‘negative’ charge localized on one face of the cluster opposite the ‘positively’ charged face of another cluster. Using U(IV) as both heterometal and molybdenum reductant afforded crystals of Mo97U10, a wheel cluster with a heptamolybdate cap on one face. Mo97U10 dissociates in solution, losing the heptamolybdate, to form Mo90U10. Using more solvent during synthesis afforded crystals of Mo90U10S4 which, instead of heptamolybdate, contains four sulfate ions. Crystals of Mo90U10S4 undergo a dehydration induced phase change where clusters form a sheet through oxide bridges. Half of the bridges are cation‐cation interactions between the uranyl oxygen atom and molybdenum, the first reported of this kind.
Chiral recognition and discrimination studies of tyrosine enantiomers on (−)‐18‐crown‐6‐tetracarboxylic acid as a chiral selector by nuclear magnetic resonance spectroscopy and docking simulations
Authors: Lee Gaeun , Adhikari Suraj , Lee Sunho , Lee Jeong Yeon , Na Yun‐Cheol , Lee Wonjae , Bang Eunjung
Published: February 2024

Considering the substantial significance of chiral biomolecules, such as amino acids, in our daily routines, we performed chiral recognition and discrimination of tyrosine (Tyr) enantiomers on (−)‐(18‐crown‐6)‐2,3,11,12‐tetracarboxylic acid [(−)‐18‐C‐6‐TA] as crown‐ether type chiral selector (CS) by nuclear magnetic resonance (NMR) spectroscopy and docking simulations. In this study, successful discrimination of the enantiomers of Tyr was achieved, as evidenced by the proton chemical shift differences (ΔΔδ) of Tyr enantiomers observed in the 1H NMR spectra with (−)‐18‐C‐6‐TA CS. We compared the results of these two techniques with the findings obtained from high performance liquid chromatography (HPLC) investigations. In both NMR and HPLC experimental and docking simulation studies, a stronger interaction between the L‐Tyr enantiomer with (−)‐18‐C‐6‐TA CS than the D‐Tyr was consistently observed. Also, the binding energy differences (ΔΔEL‐D) found in simulation data that correspond to enantioselectivity aligned well with the NMR experimental result.
Stability challenges and opportunities of NiFe‐based electrocatalysts for oxygen evolution reaction in alkaline media
Authors: Han Yujun , Wang Jingyi , Liu Yuhang , Li Tianqi , Wang Tongzhou , Li Xinyue , Ye Xinran , Li Guodong , Li Jihong , Hu Wenbin , Deng Yida
Published: February 2024

Water splitting is a critical process for the production of green hydrogen, contributing to the advancement of a circular economy. However, the application of water splitting devices on a large scale is primarily impeded by the sluggish oxygen evolution reaction (OER) at the anode. Thus, developing and designing efficient OER catalysts is a significant target. NiFe‐based catalysts are extensively researched as excellent OER electrocatalysts due to their affordability, abundant reserves, and intrinsic activities. However, they still suffer from long‐term stability challenges. To date, few systematic strategies for improving OER durability have been reported. In this review, various advanced NiFe‐based catalysts are introduced. Moreover, the OER stability challenges of NiFe‐based electrocatalysts in alkaline media, including iron segregation, structural degradation, and peeling from the substrate are summarized. More importantly, strategies to enhance OER stability are highlighted and opportunities are discussed to facilitate future stability studies for alkaline water electrolysis. This review presents a design strategy for NiFe‐based electrocatalysts and anion exchange membrane (AEM) electrolyzers to overcome stability challenges in OER, which also emphasizes the importance of long‐term stability in alkaline media and its significance for achieving large‐scale commercialization.
Autocombustion Route Derived Zinc Ferrite Nanoparticles as Chemiresistive Sensor for Detection of Alcohol Vapors
Authors: Bhagat B. , Gupta Santosh K. , Mandal D. , Bandyopadhyay R. , Mukherjee K.
Published: February 2024

Prolonged exposure to alcohol vapors can have detrimental effects on human health, potentially leading to eye irritation, dizziness, and in some cases, damage to the nervous system. The present article aims to provide a comprehensive understanding on the synthesis and characterization of zinc ferrite (ZnFe2O4) nanoparticles, as well as their interactions with a range of alcohol vapors, including methanol, ethanol, n‐propanol, and isopropanol. These alcohols differ in their molecular weight, boiling points, diffusivity, and other properties. The study reveals the semiconducting ZnFe2O4 nanoparticulate sensor‘s capability for reversible, repeatable, and sensitive detection of alcohol vapors. The sensor exhibits the highest response to ethanol within operating temperature range (225–300 °C). An attempt is made to establish a correlation between the properties of the target analytes and the observed sensing signals. Additionally, the response conductance transients of ZnFe2O4 under the exposure to the studied alcohol vapors are modeled based on the Langmuir‐Hinshelwood adsorption mechanism. The characteristic time constants obtained from this modeling are justified with respect to the properties of the analytes.
Theoretical Investigation of the Adsorbate and Potential‐Induced Stability of Cu Facets During Electrochemical CO2 and CO Reduction
Authors: Yu Henry , Govindarajan Nitish , Weitzner Stephen E. , Serra‐Maia Rui F. , Akhade Sneha A. , Varley Joel B.
Published: February 2024

The activity and product selectivity of electrocatalysts for reactions like the carbon dioxide reduction reaction (CO2RR) are intimately dependent on the catalyst's structure and composition. While engineering catalytic surfaces can improve performance, discovering the key sets of rational design principles remains challenging due to limitations in modeling catalyst stability under operating conditions. Herein, we perform first‐principles density functional calculations adopting implicit solvation methods with potential control to study the influence of adsorbates and applied potential on the stability of different facets of model Cu electrocatalysts. Using coverage dependencies extracted from microkinetic models, we describe an approach for calculating potential and adsorbate‐dependent contributions to surface energies under reaction conditions, where Wulff constructions are used to understand the morphological evolution of Cu electrocatalysts under CO2RR conditions. We identify that CO*, a key reaction intermediate, exhibits higher kinetically and thermodynamically accessible coverages on (100) relative to (111) facets, which can translate into an increased relative stabilization of the (100) facet during CO2RR. Our results support the known tendency for increased (111) faceting of Cu nanoparticles under more reducing conditions and that the relative increase in (100) faceting observed under CO2RR conditions is likely attributed to differences in CO* coverage between these facets.
Genetically Encoded Lysine Analogues with Differential Light Sensitivity for Activation of Protein Function
Authors: Wesalo Joshua S. , Liu Qingyang , Luo Ji , Shade Olivia , Deiters Alexander
Published: February 2024

Genetically encoded unnatural amino acids are versatile tools for controlling protein function, but options for regulating multiple proteins in a single experiment are limited. Here, we report the genetic encoding of two new photocaged lysine derivatives, 1‐(2‐nitrophenyl)‐ethyl lysine and nitrodibenzylfuranyl lysine, for sequential light‐activation of protein function in live cells. Nitrodibenzylfuranyl (NDBF) caging groups have a redshifted absorbance maximum and high sensitivity to light compared to the 1‐(2‐nitrophenyl)‐ethyl group (NPE), enabling selective decaging and protein activation. We characterized the responses of these new caged amino acids by optically triggering nuclear localization and firefly luciferase activity. The ability to selectively activate distinct proteins through simple light titration makes this a useful approach with broad applications.
Envirotyping can increase genomic prediction accuracy of new environments in grain sorghum trials depending on mega‐environment
Authors: Winans Noah D. , Fonseca Jales M. O. , Perumal Ramasamy , Klein Patricia E. , Klein Robert R. , Rooney William L.
Published: February 2024

Grain sorghum [Sorghum bicolor (L.) Moench] is an important crop native to Africa and grown in many subtropical and temperate regions worldwide. The variability in production environments underscores the plasticity of sorghum genotypes and provides an opportunity to predict sorghum hybrid performance in novel environments. Reaction norms informed by envirotype data can aid in modeling the differential responses of genotypes across multi‐environment trials and ultimately increase the prediction accuracies of hybrid performance. In this study, a combination of genomic and enviromic information was applied to predict grain sorghum hybrid performance across United States sorghum production environments. Seven models based on additive, dominance, environment, and envirotype effects in two forms, and their interactions were tested under three cross‐validation schemes that simulate genomic prediction scenarios encountered by breeding programs. Relationship matrices for hybrids and environments were created from molecular and envirotypic data, respectively, to predict hybrid performance under a hierarchal Bayesian framework. When predicting unobserved environments, the envirotypic reaction norm model based on typologies produced the highest prediction accuracies for every temperate environment, but results vary in the subtropical environments, which has not been demonstrated in prior enviromic research. This study also demonstrated for the first time that envirotype data can effectively define established United States sorghum production regions and may assist breeders in resource allocation. Results support using sparse hybrid trials when breeding programs apply genomic predictions. Therefore, envirotype‐assisted genomic prediction models can expand the information available to a sorghum breeding program and aid breeders in efficiently designing hybrid trials.
Advances in the Stability of Catalysts for Electroreduction of CO2 to Formic Acid
Authors: Song Dewen , Zhang Shipeng , Zhou Minjun , Wang Mingwang , Zhu Ruirui , Ning Hui , Wu Mingbo
Published: February 2024

The electroreduction of CO2 to high‐value products is a promising approach for achieving carbon neutrality. Among these products, formic acid stands out as having the most potential for industrialization due to its optimal economic value in terms of consumption and output. In recent years, the Faraday efficiency of formic acid from CO2 electroreduction has reached 90~100 %. However, this high selectivity cannot be maintained for extended periods under high currents to meet industrial requirements. This paper reviews excellent work from the perspective of catalyst stability, summarizing and discussing the performance of typical catalysts. Strategies for preparing stable and highly active catalysts are also briefly described. This review may offer a useful data reference and valuable guidance for the future design of long‐stability catalysts.
Co(O)4(N)‐type single‐atom‐based catalysts and ligand‐driven modulation of electrocatalytic properties for reducing oxygen molecules
Authors: Shin Yunseok , Lee Yeunhee , Jo Changbum , Kim Yong‐Hyun , Park Sungjin
Published: February 2024

Single‐atom‐based catalysts are intriguing electrocatalytic platforms that combine the advantages of molecular catalysts and conductive carbon‐based materials. In this work, hybrids (Co‐NrGO‐1 and Co‐NrGO‐2) were generated by wet‐reactions between organometallic complexes (Co(CH3COO)2 and Co[CH3(CH2)3CH(C2H5)COO]2, respectively) and N‐doped reduced graphene oxide at 25°C. Various characterizations revealed the formation of atomically dispersed Co(O)4(N) species in Co‐NrGO‐2. Density functional theory (DFT) calculations explained the effect of the aliphatic C7 group in Co2 on the formation processes. The Co‐NrGO‐2 hybrid showed excellent catalytic performance, such as onset (0.94 V) and half‐wave (0.83 V) potentials, for electrochemical oxygen reduction reaction (ORR). Co‐NrGO‐2 outperformed Co‐NrGO‐1, which was explained by more back donation to the antibonding orbitals of O2 from electron‐rich aliphatic groups. DFT calculations support this feature, with mechanistic investigations showing favored ORR reactions and facile breakage of double bonds in O2.
Mating strategies of Vitex negundo L. var. heterophylla (Franch.) Rehder (Lamiaceae): A mixed mating system with inbreeding depression
Authors: Zhang Qing , Zhang Jilin , Sun Xiaohan , Wang Feng , Wang Renqing , Wang Hui , Zheng Peiming
Published: February 2024

Plant reproductive ecology is one of the research hotspots in ecology. With the increasing attention paid to the conservation of plant diversity, the research on reproductive characteristics and flowering biological characteristics of more species has attracted more attention. However, plant reproduction is affected by multiple interacting factors such as pollen limitation and resource availability. Vitex negundo var. heterophylla (Franch.) Rehder (Lamiaceae) is a significant species for water and soil conservation. Previous studies have revealed its mating system by the biological characteristics of flowering and SSR markers, but its reproductive strategies remain to be further studied. We evaluated reproductive success through artificial pollination to explore the reproductive characteristics of V. negundo var. heterophylla for the first time. From the results of fruit set, there is a mixed mating system dominated by outcrossing in V. negundo var. heterophylla accompanied by self‐compatibility, and it cannot carry out autonomous selfing. Our data show the pollinator‐mediated interaction in the success of reproduction, whereas the effect of anemophily is very weak. And the seed germination rate of inbred line progenies was lower than that of hybrid progenies, which is suspected to be caused by inbreeding depression. The research will provide scientific information for the protection and conservation of V. negundo var. heterophylla from the point of view of reproduction. In sum, the results are necessary to protect animal vectors in the background of insect decline.
Development of a virtual reality system that generates prism adaptation for multiple motor units
Authors: Ishida Takashi , Higa Hiroki
Published: February 2024

Conventionally, the adaptive body area for prism adaptation (PA) has been limited to the visible area of prism glasses, especially the unilateral upper limbs. In this study, we developed a virtual reality system that extends PA's adaptive body area. This system sets the visible area of the target and introduces a symbolic representation of the body position to realize a head position adaptation task. As a result, the develped system generates PA not to individual body parts but to a collection of multiple motor units. Furthermore, experimental results in healthy subjects showed that the head position adaptation task could generate PA in the upper trunk system (The upper trunk system is defined as a system consisting of the upper trunk, head, and upper extremities) and displace it to the left anteriorly. Therefore, the head position adaptation task is expected to be effective for the postural correction of USN patients with upper trunk system tilt to the right posteriorly. Moreover, the developed system has potential applications in a wide range of fields, such as detecting cerebellar disorders.