bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structural Influence of Lone Pairs in GeP2N4, a Germanium(II) Nitridophosphate
Authors: Ambach Sebastian J. , Somers Cody , de Boer Tristan , Eisenburger Lucien , Moewes Alexander , Schnick Wolfgang 
Published: November 2022

AbstractOwing to their widespread properties, nitridophosphates are of high interest in current research. Explorative high‐pressure high‐temperature investigations yielded various compounds with stoichiometryMP2N4(M=Be, Ca, Sr, Ba, Mn, Cd), which are discussed as ultra‐hard or luminescent materials, when doped with Eu2+. Herein, we report the first germanium nitridophosphate, GeP2N4, synthesized from Ge3N4and P3N5at 6 GPa and 800 °C. The structure was determined by single‐crystal X‐ray diffraction and further characterized by energy‐dispersive X‐ray spectroscopy, density functional theory calculations, IR and NMR spectroscopy. The highly condensed network of PN4‐tetrahedra shows a strong structural divergence to otherMP2N4compounds, which is attributed to the stereochemical influence of the lone pair of Ge2+. Thus, the formal exchange of alkaline earth cations with Ge2+may open access to various compounds with literature‐known stoichiometry, however, new structures and properties.
Single Crystalline, Non‐stoichiometric Cocrystals of Hydrogen‐Bonded Organic Frameworks
Authors: Hashimoto Taito , Oketani Ryusei , Nobuoka Masaki , Seki Shu , Hisaki Ichiro 
Published: November 2022

AbstractPorous frameworks composed of non‐stoichiometrically mixed multicomponent molecules attract much attention from a functional viewpoint. However, their designed preparation and precise structural characterization remain challenging. Herein, we demonstrate that cocrystallization of tetrakis(4‐carboxyphenyl)hexahydropyrene and pyrene derivatives (CP‐Hp and CP‐Py, respectively) yields non‐stoichiometric mixed frameworks through networking via hydrogen bonding. The composition ratio of CP‐Hp and CP‐Py in the framework was determined by single crystalline X‐ray crystallographic analysis, indicating that the mixed frameworks were formed over a wide range of composition ratios. Furthermore, microscopic Raman spectroscopy on the single crystal indicates that the components are not uniformly distributed such as ideal solid solution, but are done gradationally or inhomogeneously.
Identification of Cyclohexadienyl Hydrides as Intermediates in Molybdenum‐Catalyzed Arene Hydrogenation
Authors: Hierlmeier Gabriele , Tosatti Paolo , Puentener Kurt , Chirik Paul J. 
Published: November 2022

AbstractTreatment of phosphino(imino)pyridine (PIP) molybdenum cyclooctadiene (COD) complexes [(PIP)Mo(COD)] with dihydrogen in the presence of benzene selectively furnished the molybdenum cyclohexadienyl hydrides [(PIP)MoH(η5‐C6H7)], which are precatalysts for the hydrogenation of benzene to cyclohexane. [(PIP)MoH(η5‐C6H7)] arises from a rarely observed insertion of benzene into a molybdenum‐hydride bond, a key step in the molybdenum‐catalyzed homogeneous hydrogenation of arenes. The reaction with toluene afforded a single isomer of the corresponding molybdenum cyclohexadienyl hydride while para‐xylene predominantly formed the molybdenum η6‐arene complex with the insertion product being a minor component. Addition of carbon monoxide to a cyclohexane‐d12 solution of [(PIP)MoH(η5‐C6H7)] liberated cyclohexadiene, providing experimental support for a higher kinetic barrier for the subsequent steps en route to cycloalkanes.
Structurally Defined Water‐Soluble Metallofullerene Derivatives towards Biomedical Applications
Authors: Li Yanbang , Biswas Rohin , Kopcha William P. , Dubroca Thierry , Abella Laura , Sun Yue , Crichton Ryan A. , Rathnam Christopher , Yang Letao , Yeh Yao‐Wen , Kundu Krishnendu , Rodríguez‐Fortea Antonio , Poblet Josep M. , Lee Ki‐Bum , Hill Stephen , Zhang Jianyuan 
Published: November 2022

AbstractEndohedral metallofullerenes (EMFs) are excellent carriers of rare‐earth element (REE) ions in biomedical applications because they preclude the release of toxic metal ions. However, existing approaches to synthesize water‐soluble EMF derivatives yield mixtures that inhibit precise drug design. Here we report the synthesis of metallobuckytrio (MBT), a three‐buckyball system, as a modular platform to develop structurally defined water‐soluble EMF derivatives with ligands by choice. Demonstrated with PEG ligands, the resulting water‐soluble MBTs show superb biocompatibility. The Gd MBTs exhibit superior T1 relaxivity than typical Gd complexes, potentially superseding current clinical MRI contrast agents in both safety and efficiency. The Lu MBTs generated reactive oxygen species upon light irradiation, showing promise as photosensitizers. With their modular nature to incorporate other ligands, we anticipate the MBT platform to open new paths towards bio‐specific REE drugs.
Continuous Electroformation of Gold Nanoparticles in Nanoliter Droplet Reactors
Authors: Saucedo‐Espinosa Mario Alberto , Breitfeld Maximilian , Dittrich Petra Stephanie 
Published: November 2022

AbstractGold nanoparticles (AuNPs) are employed in numerous applications, including optics, biosensing and catalysis. Here, we demonstrate the stabilizer‐free electrochemical synthesis of AuNPs inside nanoliter‐sized reactors. Droplets encapsulating a gold precursor are formed on a microfluidic device and exposed to an electrical current by guiding them through a pair of electrodes. We exploit the naturally occurring recirculation flows inside confined droplets (moving in rectangular microchannels) to prevent the aggregation of nanoparticles after nucleation. Therefore, AuNPs with sizes in the range of 30 to 100 nm were produced without the need of additional capping agents. The average particle size is defined by the precursor concentration and droplet velocity, while the charge dose given by the electric field strength has a minor effect. This method opens the way to fine‐tune the electrochemical production of gold nanoparticles, and we believe it is a versatile method for the formation of other metal nanoparticles.
Reversible Dihydrogen Activation and Catalytic H/D Exchange with Group 10 Heterometallic Complexes**
Authors: Garçon Martí , Phanopoulos Andreas , White Andrew J. P. , Crimmin Mark R. 
Published: November 2022

AbstractReaction of a hexagonal planar palladium complex featuring a [PdMg3H3] core with H2is reversible and leads to the formation of a new [PdMg2H4] tetrahydride species alongside an equivalent of a magnesium hydride co‐product [MgH]. While the reversibility of this process prevented isolation of [PdMg2H4], analogous [PtMg2H4] and [PtZn2H4] complexes could be isolated and characterised through independent syntheses. Computational analysis (DFT, AIM, NCIPlot) of the bonding in a series of heterometallic tetrahydride compounds (Ni–Pt; Mg and Zn) suggests that these complexes are best described as square planar with marginal metal‐metal interactions; the strength of which increases slightly as group 10 is descended and increases from Mg to Zn. DFT calculations support a mechanism for H2activation involving a ligand‐assisted oxidative addition to Pd. These findings were exploited to develop a catalytic protocol for H/D exchange into magnesium hydride and zinc hydride bonds.
Organocatalytic Enantioselective Pictet–Spengler Reaction of α‐Ketoesters: Development and Application to the Total Synthesis of (+)‐Alstratine A
Authors: Andres Rémi , Sun Fenggang , Wang Qian , Zhu Jieping 
Published: November 2022

AbstractWe report herein an asymmetric Pictet–Spengler reaction of α‐ketoesters. In the presence of a catalytic amount of simple alanine‐derived squaramide and p‐nitrobenzoic acid, reaction of tryptamines with methyl 2‐oxoalkanoates afforded the corresponding 1‐alkyl‐1‐methoxycarbonyl tetrahydro‐β‐carbolines (THBCs) in high yields and ee values. A primary kinetic isotope effect (KIE=4.5) using C2‐deteurium‐labelled tryptamine indicates that rearomatization through deprotonation of the pentahydro‐β‐carbolinium ion could be the rate‐ and enantioselectivity‐determining step. A concise enantioselective total synthesis of (+)‐alstratine A, a hexacyclic cagelike monoterpene indole alkaloid, featuring this reaction as a key step, was subsequently accomplished. Remeasurement of the [a]D value of the natural product indicates that natural alstratine A is dextrorotatory rather than levorotatory as it was initially reported in the isolation paper.
Efficient Multiple Domain Ligation for Proteins Using Asparaginyl Endopeptidase by Selection of Appropriate Ligation Sites Based on Steric Hindrance
Authors: Okuda Aya , Shimizu Masahiro , Inoue Rintaro , Urade Reiko , Sugiyama Masaaki 
Published: November 2022

AbstractThree domain fragments of a multi‐domain protein, ER‐60, were ligated in two short linker regions using asparaginyl endopeptidase not involving denaturation. To identify appropriate ligation sites, by selecting several potential ligation sites with fewer mutations around two short linker regions, their ligation efficiencies and the functions of the ligated ER‐60s were examined experimentally. To evaluate the dependence of ligation efficiencies on the ligation sites computationally, steric hinderances around the sites for the ligation were calculated through molecular dynamics simulations. Utilizing the steric hindrance, a site‐dependent ligation potential index was introduced as reproducing the experimental ligation efficiency. Referring to this index, the reconstruction of ER‐60 was succeeded by the ligation of the three domains for the first time. In addition, the new ligation potential index well‐worked for application to other domain ligations. Therefore, the index may serve as a more time‐effective tool for multi‐site ligations.
Synthesis of Twisted [n]Cycloparaphenylene by Alkene Insertion
Authors: Terabayashi Tomoaki , Kayahara Eiichi , Zhang Yichen , Mizuhata Yoshiyuki , Tokitoh Norihiro , Nishinaga Tohru , Kato Tatsuhisa , Yamago Shigeru 
Published: November 2022

AbstractMono‐alkene‐inserted [n]cycloparaphenylenes 1 [(ene)‐[n]CPP] with n=6, 8, and 10, mono‐ortho‐phenylene‐inserted [6]CPP 2, and di‐alkene‐insertved [n]CPP 3 [(ene)2‐[n]CPP] with n=4, 6, and 8 were synthesized by fusing CPP precursors and alkene or ortho‐ phenylene groups through coupling reactions. Single‐crystal X‐ray diffraction analyses reveal that the strips formed by the π‐surfaces of 1 and 2 exhibited a Möbius topology in the solid state. While the Möbius topology in the parent 1 and 2 in solution was lost due to the free rotation of the paraphenylene unit even at low temperatures, ene‐[6]CPP 4 with eight 1‐pyrrolyl groups preserved the Möbius topology even in solution. Despite a twist, 1 has in‐plane conjugation and possesses a unique size dependence of the electronic properties: namely, the opposite size dependency of the HOMO–LUMO energy relative to conventional π‐conjugated molecules.
Reversible Switching CuII/CuI Single Sites Catalyze High‐rate and Selective CO2 Photoreduction
Authors: Zu Xiaolong , Zhao Yuan , Li Xiaodong , Chen Runhua , Shao Weiwei , Li Li , Qiao Panzhe , Yan Wensheng , Pan Yang , Xu Qian , Zhu Junfa , Sun Yongfu , Xie Yi 
Published: November 2022

AbstractHerein, we first design a model of reversible redox‐switching metal–organic framework single‐unit‐cell sheets, where the abundant metal single sites benefit for highly selective CO2 reduction, while the reversible redox‐switching metal sites can effectively activate CO2 molecules. Taking the synthetic Cu‐MOF single‐unit‐cell sheets as an example, synchrotron‐radiation quasi in situ X‐ray photoelectron spectra unravel the reversible switching CuII/CuI single sites initially accept photoexcited electrons and then donate them to CO2 molecules, which favors the rate‐liming activation into CO2δ−, verified by in situ FTIR spectra and Gibbs free energy calculations. As an outcome, Cu‐MOF single‐unit‐cell sheets achieve near 100 % selectivity for CO2 photoreduction to CO with a high rate of 860 μmol g−1 h−1 without any sacrifice reagent or photosensitizer, where both the activity and selectivity outperform previously reported photocatalysts evaluated under similar conditions.
A comprehensive review on bio‐mimicked multimolecular frameworks and supramolecules as scaffolds for enzyme immobilization
Authors: Aggarwal Shalu , Ikram Saiqa 
Published: November 2022

AbstractImmobilization depicts a propitious route to optimize the catalytic performances, efficient recovery, minimizing autocatalysis, and also augment the stabilities of enzymes, particularly in unnatural environments. In this opinion, supramolecules and multimolecular frameworks have captivated immense attention to achieve profound controllable interactions between enzyme molecules and well‐defined natural or synthetic architectures to yield protein bioconjugates with high accessibility for substrate binding and enhanced enantioselectivities. This scholastic review emphasizes the possibilities of associating multimolecular complexes with biological entities via several types of interactions, namely covalent interactions, host–guest complexation, interactions, intra/inter hydrogen bondings, electrostatic interactions, and so forth offers remarkable applications for the modulations of enzymes. The potential synergies between artificial supramolecular structures and biological systems are the primary concern of this pedagogical review. The majority of the research primarily focused on the dynamic biomolecule‐responsive supramolecular assemblages and multimolecular architectures as ideal platforms for the recognition and modulation of proteins and cells. Embracing sustainable green demeanors of enzyme immobilizations in a quest to reinforce site‐selectivity, catalytic efficiency, and structural integrality of enzymes are the contemporary requirements of the biotechnological sectors that instigate the development of novel biocatalytic systems.
Smart tools for antimicrobial peptides expression and application: The elastic perspective
Authors: Colomina‐Alfaro Laura , Marchesan Silvia , Stamboulis Artemis , Bandiera Antonella 
Published: November 2022

AbstractIn recent years, antimicrobial peptides (AMPs) have become a promising alternative to the use of conventional and chemically synthesized antibiotics, especially after the emergence of multidrug‐resistant organisms. Thus, this review aims to provide an updated overview of the state‐of‐the‐art for producing antimicrobial peptides fused or conjugated with the elastin‐like (ELP) peculiar carriers, and that are mostly intended for biomedical application. The elastin‐like biopolymers are thermosensitive proteins with unique properties. Due to the flexibility of their modular structure, their features can be tuned and customized to improve the production of the antimicrobial domain while reducing their toxic effects on the host cells. Both fields of research faced a huge rise in interest in the last decade, as witnessed by the increasing number of publications on these topics, and several recombinant fusion proteins made of these two domains have been already described but they still present a limited variability. Herein, the approaches described to recombinantly fuse and chemically conjugate diverse AMPs with ELPs are reviewed, and the nature of the AMPs and the ELPs used, as well as the main features of the expression and production systems are summarized.
Cross‐sectional study of the quality of randomized control trials on problem‐based learning in medical education
Authors: Zhang Xiaoli , Zhang Guanran , Liu Jing , Song Xinyi , Li Manyu , Zhang Yuhua , Hao Jing , Wang Chuanzheng , Li Han 
Published: November 2022

AbstractProblem‐based learning (PBL) is increasingly being used in medical education globally, but its effectiveness in teaching remains controversial. A randomized controlled trial (RCT) is the method of choice for evaluating its effectiveness. The quality of an RCT has a significant effect on this evaluation, but to date we have not seen an assessment of the quality of RCTs for PBL. Two researchers searched MEDLINE and EMBASE for RCTs addressing PBL in medical education. The overall quality of each report was measured on a 28‐point overall quality score (OQS) based on the 2010 revised Comprehensive Standards for Reporting and Testing (CONSORT) Statement. Furthermore, to study the key factors affecting OQS more effectively, a linear regression model of those factors was established using SPSS. After literature screening, 30 RCTs were eventually included and analyzed. The median OQS was 15 (range, 7–20), which meant that half of the items in the revised 2010 CONSORT statement were poorly reported in at least 40% of the RCTs analyzed. The regression model showed that the year of publication of RCTs and the impact factors of the journals in which they were published were the main factors affecting OQS. The overall quality of reporting of RCTs on PBL teaching in medical education was not satisfactory. Some RCTs were subjectively selective in reporting certain items, leading to heterogeneity in quality. It is expected that statisticians will develop new standards more suitable for evaluating RCTs related to teaching research and that editors and peer reviewers will be required to review the relevant RCTs more strictly.
Two‐Helix Supramolecular Proteomimetic Binders Assembled via PNA‐Assisted Disulfide Crosslinking
Authors: Imiołek Mateusz , Winssinger Nicolas 
Published: November 2022

AbstractPeptidic motifs folded in a defined conformation are able to inhibit protein‐protein interactions (PPIs) covering large interfaces and as such they are biomedical molecules of interest. Mimicry of such natural structures with synthetically tractable constructs often requires complex scaffolding and extensive optimization to preserve the fidelity of binding to the target. Here, we present a novel proteomimetic strategy based on a 2‐helix binding motif that is brought together by hybridization of peptide nucleic acids (PNA) and stabilized by a rationally positioned intermolecular disulfide crosslink. Using a solid phase synthesis approach (SPPS), the building blocks are easily accessible and such supramolecular peptide‐PNA helical hybrids could be further coiled using precise templated chemistry. The elaboration of the structural design afforded high affinity SARS CoV‐2 RBD (receptor binding domain) binders without interference with the underlying peptide sequence, creating a basis for a new architecture of supramolecular proteomimetics.
Establishment of an in vitro model from the vulnerable fish species Coregonus maraena (maraena whitefish): Optimization of growth conditions and characterization of the cell line
Authors: Kaya Yagmur , Tönißen Katrin , Verleih Marieke , Rebl Henrike , Grunow Bianka 
Published: November 2022

AbstractIn this study, a cell line of the fish species Coregonus maraena was produced for the first time. C. maraena is an endangered species, and studies indicate that this fish species will be affected by further population declines due to climate change. This cell line, designated CMAfin1, has been maintained in Leibovitz L‐15 supplemented with 10% fetal bovine serum over 3 years. Both subculturing and storage (short‐term storage at −80°C and long‐term storage in liquid nitrogen) was successful. Cell morphology and growth rate were consistent from passage 10 onwards. Immunocytochemical examination of cellular proteins and matrix components confirmed the mechanical stability of the cells. Actin, fibronectin, vinculin, vimentin, and tubulin are present in the cells and form a network. In addition, the transport of molecules is ensured by the necessary proteins. Gene expression analysis showed a shift in the expressions of stem cell markers between younger and higher passages. While SOX2 and IGF1 were more highly expressed in the seventh passage, SOX9 and IGF2 expressions were significantly increased in higher passages. Therefore, the stable cell culture CMAfin1 can be used for applied analysis to further understand the cell physiology of C. maranea.
Two‐electron Oxygen Reduction Reaction on Nanocarbon Materials for Onsite H2O2 Electrochemical Synthesis: Selectivity Enhancement via Oxygen and Nitrogen co‐Doping
Authors: Lu Xingyu , Zhang Jialong , Dou Jing , Dai Xueya , Qi Wei 
Published: November 2022

AbstractProduction of hydrogen peroxide (H2O2) through the two‐electron pathway of electrocatalytic oxygen reduction reaction is a green and convenient route, which has attracted considerable attention in the field of energy and catalysis. However, the high cost of noble Pt‐based catalyst and H2O2 selectivity and stability need to be further refined for large‐scale production. Herein, we reported a O, N co‐doped mesoporous nanocarbon catalyst. The introduction of nitrogen atoms increases the electrochemically active surface area, promotes the mass transfer capacity, and reduces the impedance of electron transfer. The absolute contents of each oxygen and nitrogen functional group in the catalyst were calculated according to XPS, which reveals that pyridine nitrogen and pyrrole nitrogen might contribute most to the two‐electron electrocatalytic oxygen reduction reaction. In addition, O, N co‐doping significantly promoted the two‐electron pathway of electrocatalytic oxygen reduction, and the selectivity of hydrogen peroxide reached 93 %. The present work provides a reference for the rational design of functional groups of electrocatalysts for highly selective electrosynthesis of H2O2.
Principles of anti‐oppression: A critical analytic synthesis
Authors: Peters Harvey Charles , Luke Melissa 
Published: November 2022

AbstractThis study reports post‐structural qualitative research that critically examined, analyzed, and synthesized the anti‐oppression scholarship in counseling and related disciplines. The systematic Critical Analytic Synthesis resulted in the development of 10 principles of anti‐oppression. We discuss the principles in light of extant scholarship and identify limitations and implications.
Recent advances in solid‐state metal–air batteries
Authors: Sun Qi , Dai Lei , Luo Tingting , Wang Ling , Liang Feng , Liu Shan 
Published: November 2022

AbstractSolid‐state metal–air batteries have emerged as a research hotspot due to their high energy density and high safety. Moreover, side reactions caused by infiltrated gases (O2, H2O, or CO2) and safety issues caused by liquid electrolyte leakage will be eliminated radically. However, the solid‐state metal–air battery is still in its infancy, and many thorny problems still need to be solved, such as the large resistance of the metal/electrolyte interface and catalyst design. This review will summarize some important progress and key issues for solid‐state metal–air batteries, especially the lithium‐, sodium‐, and zinc‐based metal–air batteries, clarify some core issues, and forecast the future direction of the solid‐state metal–air batteries.