bluuebunny/crossref_metadata_2025_split huggingface dataset:
Molecular Determinant Underlying Selective Coupling of Primary G‐Protein by Class A GPCRs
Authors: Shen Qingya , Tang Xinyan , Wen Xin , Cheng Shizhuo , Xiao Peng , Zang Shao‐Kun , Shen Dan‐Dan , Jiang Lei , Zheng Yanrong , Zhang Huibing , Xu Haomang , Mao Chunyou , Zhang Min , Hu Weiwei , Sun Jin‐Peng , Zhang Yan , Chen Zhong 
Published: April 2024

AbstractG‐protein‐coupled receptors (GPCRs) transmit downstream signals predominantly via G‐protein pathways. However, the conformational basis of selective coupling of primary G‐protein remains elusive. Histamine receptors H2R and H3R couple with Gs‐ or Gi‐proteins respectively. Here, three cryo‐EM structures of H2R‐Gs and H3R‐Gi complexes are presented at a global resolution of 2.6‐2.7 Å. These structures reveal the unique binding pose for endogenous histamine in H3R, wherein the amino group interacts with E2065.46 of H3R instead of the conserved D1143.32 of other aminergic receptors. Furthermore, comparative analysis of the H2R‐Gs and H3R‐Gi complexes reveals that the structural geometry of TM5/TM6 determines the primary G‐protein selectivity in histamine receptors. Machine learning (ML)‐based structuromic profiling and functional analysis of class A GPCR–G‐protein complexes illustrate that TM5 length, TM5 tilt, and TM6 outward movement are key determinants of the Gs and Gi/o selectivity among the whole Class A family. Collectively, the findings uncover the common structural geometry within class A GPCRs that determines the primary Gs‐ and Gi/o‐coupling selectivity.
Chromium‐Induced High Covalent Co–O Bonds for Efficient Anodic Catalysts in PEM Electrolyzer
Authors: Yan Qisheng , Feng Jie , Shi Wenjuan , Niu Wenzhe , Lu Zhuorong , Sun Kai , Yang Xiao , Xue Liangyao , Liu Yi , Li Youyong , Zhang Bo 
Published: April 2024

AbstractThe proton exchange membrane water electrolyzer (PEMWE), crucial for green hydrogen production, is challenged by the scarcity and high cost of iridium‐based materials. Cobalt oxides, as ideal electrocatalysts for oxygen evolution reaction (OER), have not been extensively applied in PEMWE, due to extremely high voltage and poor stability at large current density, caused by complicated structural variations of cobalt compounds during the OER process. Thus, the authors sought to introduce chromium into a cobalt spinel (Co3O4) catalyst to regulate the electronic structure of cobalt, exhibiting a higher oxidation state and increased Co–O covalency with a stable structure. In‐depth operando characterizations and theoretical calculations revealed that the activated Co–O covalency and adaptable redox behavior are crucial for facilitating its OER activity. Both turnover frequency and mass activity of Cr‐doped Co3O4 (CoCr) at 1.67 V (vs RHE) increased by over eight times than those of as‐synthesized Co3O4. The obtained CoCr catalyst achieved 1500 mA cm−2 at 2.17 V and exhibited notable durability over extended operation periods – over 100 h at 500 mA cm−2 and 500 h at 100 mA cm−2, demonstrating promising application in the PEMWE industry.
Identification of a de novo PUF60 variant associated with craniofacial microsomia
Authors: Ogawa Takuya , Xue Jingyi , Guo Long , Inoue‐Arai Maristela Sayuri , Vendramini‐Pittoli Siulan , Zechi‐Ceide Roseli Maria , Candido‐Souza Rosana Maria , Tonello Cristiano , Brandão Michele Madeira , Ozawa Terumi Okada , Peixoto Adriano Porto , Ruiz Daniela Maria Cury Ferreira , Nakashima Tomoki , Ikegawa Shiro , Moriyama Keiji , Kokitsu‐Nakata Nancy Mizue 
Published: April 2024

AbstractCraniofacial microsomia (CFM), also known as the oculo‐auriculo‐vertebral spectrum, is a congenital disorder characterized by hypoplasia of the mandible and external ear due to tissue malformations originating from the first and second branchial arches. However, distinguishing it from other syndromes of branchial arch abnormalities is difficult, and causal variants remain unidentified in many cases. In this report, we performed an exome sequencing analysis of a Brazilian family with CFM. The proband was a 12‐month‐old boy with clinical findings consistent with the diagnostic criteria for CFM, including unilateral mandibular hypoplasia, microtia, and external auditory canal abnormalities. A heterozygous de novo nonsense variant (c.713C>G, p.S238*) in PUF60 was identified, which was predicted to be pathogenic in silico. PUF60 has been reported as a causal gene in Verheij syndrome, but not in CFM. Although the boy showed craniofacial abnormalities and developmental delay that overlapped with Verheij syndrome, the facial asymmetry with unilateral hypoplasia of the mandible observed in this case did not match the previously reported phenotypes of PUF60 variants. Our findings expand the phenotypic range of PUF60 variants that cover CFM and Verheij syndrome.
Endoscopic surgical field clarity index: An artificial intelligence‐based measure of transnasal endoscopic surgical field quality
Authors: Poche John N. , Hernandez Stephen C. , Melder Katie L. , Dunham Michael E. , Nuss Daniel W. , Fang Zhide 
Published: April 2024

Key points
Clear visualization during transnasal endoscopic surgery (TNES) is crucial for safe, efficient surgery.
The endoscopic surgical field clarity index (ESFCI) is an artificial intelligence‐enabled measure of surgical field quality.
The ESFCI allows researchers to evaluate interventions to improve visualization during TNES.
Type I [4σ+4π] versus [4σ+4π−1] Cycloaddition To Access Medium‐Sized Carbocycles and Discovery of a Liver X Receptor β‐Selective Ligand
Authors: Jiang Cheng , Hu Lingfei , Shen Shuna , Zhang Jianyu , Wang Xi , Ma Dongxu , Lu Gang , Xu Tao 
Published: April 2024

AbstractTransition‐metal‐catalyzed [4+4] cycloaddition leading to cyclooctanoids has centered on dimerization between 1,3‐diene‐type substrates. Herein, we describe a [4σ+4π−1] and [4σ+4π] cycloaddition strategy to access 7/8‐membered fused carbocycles through rhodium‐catalyzed coupling between the 4σ‐donor (benzocyclobutenones) and pendant diene (4π) motifs. The two pathways can be controlled by adjusting the solvated CO concentration. A broad range (>40 examples) of 5–6–7 and 5–6–8 polyfused carbocycles was obtained in good yields (up to 90 %). DFT calculations, kinetic monitoring and 13C‐labeling experiments were carried out, suggesting a plausible mechanism. Notably, one 5–6–7 tricycle was found to be a very rare, potent, and selective ligand for the liver X receptor β (KD=0.64 μM), which is a potential therapeutic target for cholesterol‐metabolism‐related fatal diseases.
Oxygen Vacancies Boosted Hydronium Intercalation: A Paradigm Shift in Aluminum‐Based Batteries
Authors: Huang Chengxiang , Jiang Zhou , Liu Fuxi , Li Wenwen , Liang Qing , Zhao Zhenzhen , Ge Xin , Song Kexin , Zheng Lirong , Zhou Xinyan , Qiao Sifan , Zhang Wei , Zheng Weitao 
Published: April 2024

AbstractIn aqueous aluminum‐ion batteries (AAIBs), the insertion/extraction chemistry of Al3+ often leads to poor kinetics, whereas the rapid diffusion kinetics of hydronium ions (H3O+) may offer the solution. However, the presence of considerable Al3+ in the electrolyte hinders the insertion reaction of H3O+. Herein, we report how oxygen‐deficient α‐MoO3 nanosheets unlock selective H3O+ insertion in a mild aluminum‐ion electrolyte. The abundant oxygen defects impede the insertion of Al3+ due to excessively strong adsorption, while allowing H3O+ to be inserted/diffused through the Grotthuss proton conduction mechanism. This research advances our understanding of the mechanism behind selective H3O+ insertion in mild electrolytes.
Novel RP‐HPLC method for estimation of a newly developed combination of tizanidine and etoricoxib in rat plasma: Eight criteria for greens evaluation
Authors: Assirey Eman A. , Ahmed Hoda A. , AL‐Faze Rawan , Amin M. S. , Mahgoub Samar M. , Abo El‐Ela Fatma I. , Mohamed Mahmoud A. 
Published: April 2024

AbstractA novel environmentally friendly reversed‐phase high‐performance liquid chromatography (RP‐HPLC) method has been effectively validated for simultaneously measuring a prospective conjunction of tizanidine (TIZ) and etoricoxib (ETC), the combined medicine, in rat plasma. The technique employs diclofenac potassium as the internal standard, guaranteeing dependable and precise outcomes. This study aimed to assess the impact of the suggested combination therapy on treating inflammation resulting from rheumatoid arthritis (RA) in a rat model. The procedure was performed using an Agilent series 1200 model HPLC apparatus. The chromatographic conditions consist of isocratic elution mode, C18 column with dimensions of 150 mm × 4.6 mm × 5 µm, flow rate of 1.5 mL/min, wavelength of 230 nm, temperature of 50°C, and injection volume of 10 µL. The elution was performed using a mobile phase consisting of a phosphate buffer with a pH of 3.5 and acetonitrile in a ratio of 80:20 v/v. Calibration curves were conducted for TIZ and ETC within the 1–50 µg/mL range, demonstrating linear trends with R2 values over 0.999. The effectiveness and eco‐friendliness of the proposed method were evaluated using eight separate environmentally conscious metrics. The addition of TIZ and ETC to arthritic rodents amplified these effects significantly. Furthermore, TIZ and ETC significantly reduced serum levels in arthritic rodents, and safety investigations revealed normal complete blood count, liver, and renal functions. TIZ and ETC appear to have antiarthritic, anti‐inflammatory, and safe combinations, making them viable future treatment options for RA that are also safe and efficacious. Following validation by United States Food and Drug Administration (US‐FDA) rules, all goods met the criteria.
Reactivity of a Linear 2‐Germapropadiene with Acids, Ketones, and Amines
Authors: Sugamata Koh , Asakawa Teppei , Minoura Mao 
Published: April 2024

AbstractThe reactivity of an isolable 2‐germapropadiene with acids, ketones, and amines was investigated. The reactions of 2‐germapropagiene 1 with hydrogen chloride and acetic acid afforded the corresponding dichlorogermane (2) and diacetoxygermane (3), respectively, indicating that the central germanium atom of 1 is electrophilic. The reaction of 1 with benzaldehyde proceeds via a formal [2+2] cycloaddition to afford the corresponding spiro compound (4). Moreover, 1 reacts smoothly with acetone to furnish germane 5, which contains a six‐membered ring involving two acetone molecules. Furthermore, 1 undergoes N−H bond insertion with methylamine or aniline to afford diamino germanes 7 and 8, respectively. The reaction of 1 with urea selectively afforded the corresponding N−H−insertion product (8).
Breaking Cycles: Saponification‐Enhanced NMR Fingerprint Matching for the Identification and Stereochemical Evaluation of Cyclic Lipodepsipeptides from Natural Sources
Authors: Muangkaew Penthip , Prasad Durga , De Roo Vic , Verleysen Yentl , Zhou Lu , De Mot René , Höfte Monica , Madder Annemieke , Geudens Niels , Martins José C. 
Published: April 2024

AbstractWe previously described NMR based fingerprint matching with peptide backbone resonances as a fast and reliable structural dereplication approach for Pseudomonas cyclic lipodepsipeptides (CLiPs). In combination with total synthesis of a small library of configurational CLiP congeners this also allows unambiguous determination of stereochemistry, facilitating structure‐activity relationship studies and enabling three‐dimensional structure determination. However, the on‐resin macrocycle formation in the synthetic workflow brings considerable burden and limits universal applicability. This drawback is here removed altogether by also transforming the native CLiP into a linearized analogue by controlled saponification of the ester bond. This eliminates the need for macrocycle formation, limiting the synthesis effort to linear peptide analogues. NMR fingerprints of such linear peptide analogues display a sufficiently distinctive chemical shift fingerprint to act as effective discriminators. The approach is developed using viscosin group CLiPs and subsequently demonstrated on putisolvin, leading to a structural revision, and tanniamide from Pseudomonas ekonensis COR58, a newly isolated lipododecapeptide that defines a new group characterized by a ten‐residue large macrocycle, the largest to date in the Pseudomonas CLiP portfolio. These examples demonstrate the effectiveness of the saponification‐ enhanced approach that broadens applicability of NMR fingerprint matching for the determination of the stereochemistry of CLiPs.
Rapid Electronic Transport Channel of Co‐P with Mo in a Heterostructure Embedded with P, N Dual Doped Porous Carbon for Electrocatalytic Oxygen and Hydrogen Evolution
Authors: Dey Tapan , Rajput Anubha , Jhaa Gaurav , Matsagar Babasahab M. , Chen Norman C.‐R , Kumar Nitish , Salunkhe Rahul , Wu Kevin C.‐W. , Chakraborty Biswarup , Dutta Saikat 
Published: April 2024

AbstractWe developed a molybdenum (Mo)‐doped cobalt (Co)‐heterostructure embedded on a phosphorous (P) and nitrogen (N) dual‐doped porous carbon which exhibits an intrinsic electronic transport channel of Co to Mo and P. The P,Mo,O−Co/PNC/NF (NF=Nickel foam) electrode offers 335 mV overpotential at 10 mA cm−2 in OER as compared with PMA‐ZIF67‐NC/NF and ZIF67‐NC/NF electrode with an overpotential of 357 and 373 mV respectively. Linear sweep voltammetry (LSV) of overall water splitting (OWS) supports that the current density gradually increased at a cell potential of 1.6 V with a maximum of 40 mA with a corresponding cell potential of 1.79 V at a current density of 10 mA cm−2. Density functional theory (DFT) calculations for water adsorption on optimized [111] surface of Co, CoMo, and CoMoP2 with adsorbed H2O and corresponding lattice determine the electron density difference of [111] surface with adsorbed H2O for Eads (eV) 4.23 corresponds to adsorption energy for CoMoP2. XANE‐EXAFS spectroscopy of P,Mo,O−Co/PNC at Co K edge and Mo K edge suggests the presence of higher valence of both Cox+ and Mox+ without metallic Co and Mo and Co−P and Mo−P bonds as major structural units due to phosphidation as determined by R‐space FT‐EXAFS spectra.
Synthesis, docking study, and antitumor evaluation of benzamides and oxadiazole derivatives of 3‐phenoxybenzoic acid as VEGFR‐2 inhibitors
Authors: Heriz Mohammad H. , Mahmood Ammar A. R. , Yasin Salem R. , Saleh Khaled M. , AlSakhen Mai F. , Kanaan Sana I. , Himsawi Nisreen , Saleh Abdulrahman M. , Tahtamouni Lubna H. 
Published: April 2024

AbstractCurrent chemotherapeutic agents have several limitations, including lack of selectivity, the development of undesirable side effects, and chemoresistance. As a result, there is an unmet need for the development of novel small molecules with minimal side effects and the ability to specifically target tumor cells. A new series of 3‐phenoxybenzoic acid derivatives, including 1,3,4‐oxadiazole derivatives (4a–d) and benzamides derivatives (5a–e) were synthesized; their chemical structures were confirmed by Fourier‐transform infrared spectroscopy, 1H nuclear magnetic resonance (NMR), 13C NMR, and mass spectra; and various physicochemical properties were determined. The antiproliferative activities of the new derivatives were evaluated by means of the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay. Three compounds (4b, 4c, and 4d) exhibited cytotoxicity against two of the three cell lines tested, five compounds (3, 4a, 5a, 5b, and 5e) were toxic to one cell line, while two compounds (5c and 5d) were not cytotoxic to any of the three cell lines tested in the current study. Based on docking scores, MTT assay findings, and vascular endothelial growth factor receptor 2 (VEGFR‐2) kinase activity data, Compound 4d was selected for further biological investigation. Flow cytometry was used to determine the mode of cell death (apoptosis vs. necrosis) and the effect on cell cycle progression. Compound 4d arrested HepG2 hepatocellular carcinoma cells in the G2/M phase and activated both the intrinsic and extrinsic apoptosis pathways. In conclusion, Compound 4d has shown promising results for future research as a potent VEGFR‐2 tyrosine kinase inhibitor.
Methylation of phase II metabolites of endogenous anabolic androgenic steroids to improve analytical performance
Authors: Pfeffer Sandra , Gmeiner Guenter , Forsdahl Guro 
Published: April 2024

AbstractThe study of intact phase II metabolites of endogenous anabolic androgenic steroids (EAAS) gives important information about metabolism and has the potential to improve the detection of doping with testosterone. For analysis with liquid chromatography–mass spectrometry (LC‐MS), chemical derivatization at the steroid moiety is a technique to improve the positive ionization efficiency of glucuronidated/sulfated EAAS under collision‐induced dissociation (CID) conditions. However, regarding the chromatographic performance, there are still challenges to address, for example, poor peak shape, which is mainly caused by nondefined adsorption in the chromatographic system. Here, we show a novel derivatization technique for the analysis of selected phase II metabolites of EAAS, where the acidic moiety of the glucuronide/sulfate is methylated with different methylation reagents to reduce nondefined adsorption. The methylation reagent trimethylsilyl‐diazomethane (TMSD) was preferred over the other tested reagents methyl iodide (MeI) and dimethyl sulfate (DMS). Glucuronidated and sulfated testosterone and epitestosterone were methylated, and their chromatographic performance and CID ion mass spectra obtained in positive ionization mode were investigated. The peak width and peak height were significantly improved for all substances. Methylated testosterone sulfate showed the best results with a 3.5 times narrower peak and 14 times increased intensity compared with underivatized testosterone sulfate. Furthermore, CID ion mass spectra obtained in positive ionization mode showed product ions characteristically for the steroidal backbone for all substances. This preliminary study shows the potential of methylation as a supplementary derivatization technique, which can assist in the development of more sensitive methods due to the improvements in method performance.
Alternatively Connected Corrole‐Porphyrin Multimetallic Complexes: Synthesis, Structure, and Properties
Authors: Harpal  , Murugavel Muthuchamy , Rai Jyoti , Panini Piyush , Reddy R. V. Ramana , Thakur Parikshit , Sankar Jeyaraman 
Published: April 2024

AbstractSynthetic multimetallic porphyrinoids are potential candidates in catalysis, molecular magnetism and as modern optoelectronic materials. Introducing electronic heterogenity in these multi‐porphyrinoids shall bring in novel electronic and redox characteristics. In this direction, herein we report four discrete Corrole‐Porphyrin‐Corrole C[10] ⋅ P[5,15] ⋅ C[10] hybrids that have both corrole and porphyrin units covalently connected together. Metal ions in diverse oxidation states have been incorporated into respective cores to achieve homo and heterotrinuclear metal complexes. Selective metalation at the porphyrin and corrole cores was achieved by step‐wise insertion of Zn(II)/Cu(II), Zn(II)/Ga(III) and Cu(II)/Cu(II) ions to suit the dianionic and trianionic pockets, respectively. Single crystal X‐ray diffraction studies reveal the solid‐state structural evidence for both homo‐, and hetero‐trinuclear metal complexes. The Zn(II) and Ga(III) moieties have two distinct geometries in the molecular assembly. The geometry of Zn(II) at the porphyrin core is a perfect square planar, whereas the Ga(III) geometry at the corrole is square pyramidal with pyridine as an axial ligand. In case of homotrinuclear Cu(II) complex, the Cu(II) ions adopt square planar geometry irrespective of the core. Similar to all porphyrin trimers, C[10] ⋅ P[5,15] ⋅ C[10] trimers exhibit significant excitonic coupling between corrole and porphyrin units in the absorption spectra. The cyclic voltametric investigations also reveal electronic coupling between the individual chromophores despite the non‐coplanar arrangement amongst the individual macrocycles.
Level of diagnostic agreement in musculoskeletal shoulder diagnosis between remote and face‐to‐face consultations: A retrospective service evaluation
Authors: Cockburn Louise , Baer Gill , Rhodes Jenna 
Published: April 2024

AbstractBackground and AimsTo determine the level of diagnostic agreement between remote and face‐to‐face consultation in assessing shoulder complaints.MethodsA retrospective service evaluation with three groups of patient data; those assessed only face‐to‐face (group 1), remotely then face‐to‐face (group 2), remotely only (group 3). Patient data were extracted from 6 secondary care shoulder Advanced Physiotherapy Practitioner's (APPs) records, covering six sites. Three‐hundred‐and‐fifty‐nine sets of patient data were included in the final evaluation. The main outcome measure was the percentage of agreement between diagnosis at initial and follow‐up consultation, when assessed by APPs across the three groups. A Pearson χ2 test was used to assess the relationship between the method of consultation and the level of diagnostic agreement. Diagnoses were categorized as either the same, similar, or different by an independent APP. Secondary outcome measures investigated whether age or the length of time between appointments had any effect in determining the level of diagnostic concordance.ResultsThere was exact agreement of 77.05% and 85.52% for groups 1 and 3, respectively, compared with 34.93% for patient data in group 2. Similar clinical impressions across both initial and follow‐up were seen 16.39% of the time in group 1, 7.24% of the time in group 3, and 36.99% in group 2. Lastly, the percentage of times a diagnosis was changed between initial and review appointments occurred in only 6.56% of group 1 contacts, 7.24% of group 3 contacts, but 28.08% of the time in group 2.ConclusionThere was a large mismatch in the diagnosis of musculoskeletal shoulder complaints, when patients are initially assessed remotely and then followed‐up in‐person. This has implications for the future provision of shoulder assessment in physiotherapy.
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Authors: Li Xue , Wu Shuo‐En , Wu Di , Zhao Tianxiang , Lin Pei , Shi Zhifeng , Tian Yongtao , Li Xinjian , Zeng Longhui , Yu Xuechao 
Published: April 2024

The in‐situ integrated PtSe2/Ge Schottky junction array demonstrates an ultrabroadband detection range up to 4.6 μm with a large detectivity.image