bluuebunny/crossref_metadata_2025 huggingface dataset:
Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence
Authors: Wu Tianhui , Jiang Xingxing , Duanmu Kaining , Wu Chao , Lin Zheshuai , Huang Zhipeng , Humphrey Mark G. , Zhang Chi
Published: December 2023

Considerable effort has been invested in the development of non‐centrosymmetric (NCS) inorganic solids for ferroelectricity‐, piezoelectricity‐ and, particularly, optical nonlinearity‐related applications. While great progress has been made, a persistent problem is the difficulty in constructing NCS materials, which probably stems from non‐directionality and unsaturation of the ionic bonds between metal counter‐cations and covalent anionic modules. We report herein a secondary‐bond‐driven approach that circumvents the cancellation of dipole moments between adjacent anionic modules that has plagued second‐harmonic generation (SHG) material design, and which thereby affords a polar structure with strong SHG properties. The resultant first NCS counter‐cation‐free iodate, VO2(H2O)(IO3) (VIO), a new class of iodate, crystallizes in a polar lattice with
VO2(H2O)(IO3)] zigzag chains connected by weak hydrogen bonds and intermolecular forces. VIO exhibits very large SHG responses (18 × KH2PO4 @ 1200 nm, 1.5 × KTiOPO4 @ 2100 nm) and sufficient birefringence (0.184 @ 546 nm). Calculations and crystal structure analysis attribute the large SHG responses to consistent polarization orientations of the
VO2(H2O)(IO3)] chains controlled by secondary bonds. This study highlights the advantages of manipulating the secondary bonds in inorganic solids to control NCS structure and optical nonlinearity, affording a new perspective in the development of high‐performance NLO materials.
Design eines Phosphor‐zentrierten Disbiradikals
Authors: Rosenboom Jan , Taube Florian , Teichmeier Leon , Villinger Alexander , Reinhard Maik , Demeshko Serhiy , Bennati Marina , Bresien Jonas , Corzilius Björn , Schulz Axel
Published: December 2023

Phosphor‐zentrierte Disbiradikale, in denen die Radikalzentren als einzelne Spin‐Dubletts mit schwacher Spin‐Spin‐Wechselwirkung vorliegen, waren bisher nicht bekannt. Ausgehend von Monoradikalen des Typs [⋅P(μ‐NTer)2P−R] ist es uns nun gelungen, zwei monoradikalische Phosphorzentren durch geeignete Wahl eines Linkers zu verknüpfen. Zu diesem Zweck wurde das Biradikal [⋅P(μ‐NTer)2P⋅] (1) mit 1,6‐Dibromhexan umgesetzt, wodurch die bromierte Spezies {Br[P(μ‐NTer)]2}2C6H12 (3) entstand. Die anschließende Reduktion mit KC8 führte zur Bildung des Disbiradikals {⋅[P(μ‐NTer)]2}2C6H12 (4), das sich durch einen großen Abstand zwischen den radikalischen Phosphorzentren im Festkörper auszeichnet und mit annähernd 100 % den bisher höchsten Biradikalcharakter in einem P‐zentrierten Biradikal aufweist. Die EPR‐spektroskopische Untersuchung ergab ein Drei‐Linien‐Signal in Lösung mit einer erheblich größeren Austauschwechselwirkung als es aufgrund der Molekülstruktur im Einkristall zu erwarten wäre. Quantenchemische Berechnungen ergaben einen hochdynamischen Konformationsraum; demnach können sich die beiden Radikalstellen in Lösung mit einem viel geringeren Abstand einander nähern. Die weitere Reduktion von 4 führte zur Bildung eines Kaliumsalzes mit dem ersten strukturell charakterisierten P‐zentrierten distonischen Radikalanion (5−). Außerdem konnte 4 für die Aktivierung kleiner Moleküle eingesetzt werden.
Polyoxometalate‐Nanozyme‐Integrated Nanomotors (POMotors) for Self‐Propulsion‐Promoted Synergistic Photothermal‐Catalytic Tumor Therapy
Authors: Tang Minglu , Ni Jiatong , Yue Zhengya , Sun Tiedong , Chen Chunxia , Ma Xing , Wang Lei
Published: December 2023

Enzyme‐powered nanomotors have demonstrated promising potential in biomedical applications, especially for catalytic tumor therapy, owing to their ability of self‐propulsion and bio‐catalysis. However, the fragility of natural enzymes limits their environmental adaptability and also therapeutic efficacy in catalysis‐enabled tumor therapy. Herein, polyoxometalate‐nanozyme‐based light‐driven nanomotors were designed and synthesized for targeted synergistic photothermal‐catalytic tumor therapy. In this construct, the peroxidase‐like activity of the P2W18Fe4 polyoxometalates‐based nanomotors can provide self‐propulsion and facilitate their production of reactive oxygen species thus killing tumor cells, even in the weakly acidic tumor microenvironment. Conjugated polydopamine endows the nanomotors with the capability of light‐driven self‐propulsion behavior. After 10 min of NIR (808 nm) irradiation, along with the help of epidermal growth factor receptor antibody, the targeted accumulation and penetration of nanomotors in the tumor enabled highly efficient synergistic photothermal‐catalytic therapy. This approach overcomes the disadvantages of the intrinsically fragile nature of enzyme‐powered nanomotors in physiological environments and, more importantly, provides a motility‐behavior promoted synergistic anti‐tumor strategy.
Palladium‐Catalyzed Regioselective Synthesis of 2‐SF5‐Indenols and Further Derivatizations
Authors: Popek Lucas , Cihan Murat , Blanchard Nicolas , Bizet Vincent
Published: December 2023

A palladium‐catalyzed synthesis of 2‐SF5‐indenols has been developed by reacting commercially available boronic acid derivatives and readily accessible SF5‐alkynes. The present methodology is fully regioselective thanks to the intrinsic polarization of SF5‐alkynes. A selection of downstream functionalizations has been performed to highlight the versatility of 2‐SF5‐indenols and indenones as platforms for the design of more complex SF5‐containing molecules.
Discrimination of Disaccharide Isomers of Different Glycosidic Linkages Using a Modified MspA Nanopore
Authors: Zhang Shanyu , Cao Zhenyuan , Fan Pingping , Sun Wen , Xiao Yunqi , Zhang Panke , Wang Yuqin , Huang Shuo
Published: December 2023

Disaccharides are composed of two monosaccharide subunits joined by a glycosidic linkage in an α or β configuration. Different combinations of isomeric monosaccharide subunits and different glycosidic linkages result in different isomeric disaccharide products. Thus, direct discrimination of these disaccharide isomers from a mixture is extremely difficult. In this paper, a hetero‐octameric Mycobacterium smegmatis porin A (MspA) nanopore conjugated with a phenylboronic acid (PBA) adapter was applied for disaccharide sensing, with which three most widely known disaccharides in nature, including sucrose, lactose and maltose, were clearly discriminated. Besides, all six isomeric α‐D‐glucopyranosyl‐D‐fructoses, differing only in their glycosidic linkages, were also well resolved. Assisted by a custom machine learning algorithm, a 0.99 discrimination accuracy is achieved. Nanopore discrimination of disaccharide isomers with different glycosidic linkages, which has never been previously demonstrated, is inspiring for nanopore saccharide sequencing. This sensing capacity was also applied in direct identification of isomaltulose additives in a commercial sucrose‐free yogurt, from which isomaltulose, lactose and L‐lactic acid were simultaneously detected.
Single Zn Atoms with Acetate‐Anion‐Enabled Asymmetric Coordination for Efficient H2O2 Photosynthesis
Authors: Li Yunxiang , Guo Yan , Fan Guilan , Luan Deyan , Gu Xiaojun , Lou Xiong Wen (David)
Published: December 2023

Exploring unique single‐atom sites capable of efficiently reducing O2 to H2O2 while being inert to H2O2 decomposition under light conditions is significant for H2O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single‐Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single‐Zn sites on CN, forming asymmetric Zn−N3O moiety on CN (denoted as CN/Zn−OAc), in contrast to the obtained Zn−N4 sites when sulfate (SO4) is adopted (CN/Zn−SO4). Both experimental and theoretical investigations demonstrate that the Zn−N3O moiety exhibits higher intrinsic activity for O2 reduction to H2O2 than the Zn−N4 moiety. This is attributed to the asymmetric N/O coordination, which promotes the adsorption of O2 and the formation of the key intermediate *OOH on Zn sites due to their modulated electronic structure. Moreover, it is inactive for H2O2 decomposition under both dark and light conditions. As a result, the optimized CN/Zn−OAc catalyst exhibits significantly improved photocatalytic H2O2 production activity under visible light irradiation.
Rational Design of a Phosphorus‐Centered Disbiradical
Authors: Rosenboom Jan , Taube Florian , Teichmeier Leon , Villinger Alexander , Reinhard Maik , Demeshko Serhiy , Bennati Marina , Bresien Jonas , Corzilius Björn , Schulz Axel
Published: December 2023

Phosphorus‐centered disbiradicals, in which the radical sites exist as individual spin doublets with weak spin‐spin interaction have not been known so far. Starting from monoradicals of the type [⋅P(μ‐NTer)2P−R], we have now succeeded in linking two such monoradical phosphorus centers by appropriate choice of a linker. To this end, biradical [⋅P(μ‐NTer)2P⋅] (1) was treated with 1,6‐dibromohexane, affording the brominated species {Br[P(μ‐NTer)]2}2C6H12 (3). Subsequent reduction with KC8 led to the formation of the disbiradical {⋅[P(μ‐NTer)]2}2C6H12 (4) featuring a large distance between the radical phosphorus sites in the solid state and formally the highest biradical character observed in a P‐centered biradical so far, approaching 100 %. EPR spectroscopy revealed a three‐line signal in solution with a considerably larger exchange interaction than would be expected from the molecular structure of the single crystal. Quantum chemical calculations revealed a highly dynamic conformational space; thus, the two radical sites can approach each other with a much smaller distance in solution. Further reduction of 4 resulted in the formation of a potassium salt featuring the first structurally characterized P‐centered distonic radical anion (5−). Moreover, 4 could be used in small molecule activation.
Cocrystallization‐driven Formation of fcc‐based Ag110 Nanocluster with Chinese Triple Luban Lock Shape
Authors: Qu Mei , Zhang Fu‐Qiang , Zhang Gai‐Li , Qiao Miao‐Miao , Zhao Li‐Xiang , Li Shi‐Li , Walter Michael , Zhang Xian‐Ming
Published: December 2023

Luban locks with mortise and tenon structure have structural diversity and architectural stability, and it is extremely challenging to synthesize Luban lock‐like structures at the molecular level. In this work, we report the cocrystallization of two structurally related atom‐precise fcc silver nanoclusters Ag110(SPhF)48(PPh3)12 (Ag110) and Ag14(μ6‐S)(SPhF)12(PPh3)8 (Ag14). It is worth noting that the Ag110 cluster is the first compound to simulate the complex Luban lock structure at the molecular level. Meanwhile, Ag110 is the largest known fcc‐based silver nanocluster, so far, there is no precedent for fcc silver nanocluster with more than 100 silver atoms. DFT calculations show that Ag110 is a 58‐electron superatom with an electronically closed shell1S21P61D102S21F142P61G18. Ag110⋅Ag14 can rapidly catalyze the reduction of 4‐nitrophenol within 4 minutes. In addition, Ag110 presents clear structural evidence to reveal the critical size and mechanism of the transformation of metal core from fcc stacking to quasi‐spherical superatom. This research work provides an important structural model for studying the nucleation mechanism and structural assembly of silver nanoclusters.
Selective Synthesis and Functionalization of an Acyclic Methylene‐Bridged‐Arene Trimer in a Cage
Authors: Takezawa Hiroki , Iizuka Kenta , Fujita Makoto
Published: December 2023

Arene‐formaldehyde condensation is a versatile reaction for producing various oligomeric/polymeric materials. However, the precise control of oligomerization degree is still challenging because the starting materials and intermediates have similar reactivities. Here, we demonstrate the selective synthesis of a methylene‐bridged arene trimer using the confined cavity of a coordination cage. The limited space of the cavity prevents unregulated polymerization. The confinement effect for the kinetic protection is also demonstrated by the subsequent site‐selective iodination of the trimer product within the cage.
Unveiling the potential of Pd(II)‐covalent organic polyimide framework in Suzuki coupling reactions: A study on synthesis, characterization, and catalytic efficiency
Authors: Moeinpour Farid
Published: December 2023

In this research, a highly effective heterogeneous Pd catalytic system was conceived by immobilizing Pd(II) onto a substrate composed of covalent organic polyimide frameworks (PI‐COF). The synthesized catalyst underwent comprehensive characterization using techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 adsorption analysis (Brunauer–Emmett–Teller [BET]), Fourier transform infrared (FT‐IR), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission spectroscopy (ICP‐AES). Subsequently, the catalytic activity of this immobilized Pd catalyst was explored in the context of the Suzuki reaction. The reactions at 70°C up to 1 h under a normal atmosphere in water result in biaryls at good to excellent yields (>90%). More importantly, the leaching of Pd(II) during the reaction process could be negligible (about 0.5 ppm), which is crucially important when preparing bioactive species. The loading of Pd(II) ions on the PI‐COF was 0.49 mmol/g. The catalyst exhibited exceptional performance, demonstrating remarkable efficacy in catalyzing a wide range of aryl halides (excluding aryl chlorides) when reacted with phenylboronic acid under environmentally friendly reaction conditions. Notably, the catalyst exhibited robust recyclability, retaining its catalytic activity throughout 5 reaction cycles without any significant decrease.
Exploring the antimicrobial, antioxidant and cytotoxic activities of organyltellurium (IV) complexes incorporating 2‐hydroxy‐1‐naphthaldehyde schiff base ligand: Synthesis, spectroscopic investigations and theoretical studies
Authors: Dalal Mahak , Devi Jai , Antil Nidhi , Kumar Binesh , Verma Yogesh Kumar , Kumar Subodh , Wati Mukhan , Garg Sapana
Published: December 2023

In this study, Schiff base ligand 1,1′‐((propane‐1,3‐diylbis [azaneylylidene]) bis (methaneylylidene))bis (naphthalen‐2‐ol) based Organyltellurium (IV) complexes were synthesized with formulae C32H27ClN2O3Te (5a)\C31H25ClN2O3Te (5b)\C32H27ClN2O3Te (5c)\ C39H34N2O4Te (5d)\ C37H30N2O4Te (5e)\ C39H34N2O4Te (5f) for acquiring a potential therapeutic agent. The synthesized compounds were characterized by ultraviolet–visible (UV–Vis), FT‐IR, 1H‐NMR, 13C‐NMR, mass spectrometry, molar conductance, elemental analysis, powder X‐ray diffraction and EDAX, which states that the tetradentate Schiff base ligand (HNDP) coordinated via oxygen and nitrogen atom with tellurium giving hexa‐coordinated tellurium (IV) complexes. The thermal features of the ligand and complexes were studied using thermal (TGA and DTG) technique. The biochemical behavior of the Schiff base and its complexes was assessed by examining their reactivity against various microbial strains, DPPH free radicals as well as normal and cancer cells. The complex 5c exhibited the highest inhibition activity against bacterial strains while complex 5f showed the strongest inhibition activity against fungal strains. Complexes 5e and 5f displayed the most effective suppression of DPPH free radicals. The results of in vitro cytotoxicity study revealed that complex 5a demonstrated moderate cytotoxic effect on the L929 cell lines. Complex 5c displayed a significant cytotoxic effect on the PC3 cell line. Moreover, complex 5a, 5c and 5e exhibited the best cytotoxic activity against the Saos‐2 cell line. Additionally, the structural forms of synthesized compounds were elucidated by DFT study. Furthermore, pharmacokinetic ADMET properties were estimated for their drug similarity behavior. The results advocate that complexes can be utilized as biological drugs.
The psychometric properties and treatment outcomes associated with two measures of the adult therapeutic alliance using naturalistic data
Authors: Mahon Daryl , Minami Takuya , Brown (G. S.) Jeb
Published: December 2023

Purpose

This is the first of two articles that examine the psychometric properties and treatment outcomes associated with measures of the therapeutic alliance collected in naturalistic settings rather than clinical trials. These articles break new ground in understanding the relationship between measures of alliance and treatment outcome by performing detailed item analyses in order to assess the psychometric properties of each individual item, its propensity to change from session to session and its utility in predicting change in the outcome measure.

Methods

Data were taken from the ACORN database for adults attending for psychotherapy treatment in naturalistic settings (N = 147,399). The sample, the largest to date, included only those completing both an alliance measure and an outcome measure at every session. Two sets of three different alliance items are used across three different treatment populations: general outpatient, substance use, and severe and persistent mental health difficulties. To investigate this possibility, the psychometric properties of each item were evaluated, including factor analysis, likelihood of change over time in treatment and correlations between changes in alliance and magnitude of client‐reported improvement in therapy. The predictive validity of each individual item is compared with the predictive validity of their respective three‐item measures. The problem of alliance scores being heavily skewed in a positive direction and the resulting lack of variability from session to session is addressed by categorising change in alliance as same, better or worse, regardless of the magnitude of change.

Results

Findings tended to differ from those in clinical trials, with the last alliance score being most predictive of outcome. In this data set, the alliance accounted for, at most, 2% of the variance in outcomes. Measures of the therapeutic alliance demonstrate ceiling effects, and the alliance–outcome correlation is far from linear. Change in alliance score, rather than a single assessment, is more predictive of outcome, regardless of the magnitude of change in the alliance measure, with effect sizes of up to 50% more for those who rated the alliance as worse than for those rating it as no change or better.

Conclusion

Therapists using therapeutic alliance questionnaires will benefit from being aware of how the psychometric properties of alliance measures impact outcomes. Even the smallest drop in alliance is predictive of significant clinically meaningful differences. Implications for practice, training and research are considered.
Membrane‐Based Preparation Process and Antioxidant and Anti‐AGEs Activities of a Novel Propolis Ultrafiltrate
Authors: Liang Xiao‐lu , Wu Yong‐lin , Chen Yu‐jia , Zhang Jia‐min , He Jian , Yuan Min , Pan Tian‐ling , Pineda Miguel A. , Li Kun‐ping
Published: December 2023

Propolis is one functional supplement with hundreds of years of usage. However, it's rarely consumed directly for its resinous property. Herein, a pre‐treated process which can remove the impurity while preserve its bioactivities is needed to maximise its therapeutic opportunities. In the present study, a membrane‐based ultrafiltration process was developed on a KM1812‐NF experimental instrument. Using Brazilian green propolis as testing material, all experimental steps and parameters were sequentially optimized. In addition, a mathematical model was developed to fit the process. As a result, the optimum solvent was 60 % ethanol adjusted to pH 8–9, while the optimum MWCO (molecular weight cut‐off) value of membrane was 30 KDa. The membrane filtration dynamic model fitted with the function y=(ax+b)/(1+cx+dx2). The resulting propolis ultrafiltrate from Brazilian green propolis, termed P30K, contains the similar profile of flavonoids and phenolic acids as raw propolis. Meanwhile, the ORAC (oxygen radical absorbance capacity) value of P30K is 11429.45±1557.58 μM TE/g and the IC50 value of inhibition of fluorescent AGEs (advanced glycation end products) formation is 0.064 mg/mL. Our work provides an innovative alternative process for extraction of active compounds from propolis and reveals P30K as an efficient therapeutic antioxidant.
Four New Steroidal Saponins from the Roots of Dracaena cambodiana with NO Production Inhibition Activity in LPS Activated RAW 264.7 Cells
Authors: Yen Pham Hai , Tai Bui Huu , Hoang Nguyen Huy , Dung Duong Thi , Nhiem Nguyen Xuan , Yen Duong Thi Hai , Huong Phan Thi Thanh , Dung Nguyen Viet , Hang Dan Thi Thuy , Ha Nguyen Thi , Trang Do Thi , Thu Vu Kim , Kiem Phan Van
Published: December 2023

Seven steroidal saponins including three new 16,23‐cyclocholestanes (1‐3) and one new pregane (4) were isolated from the roots of Dracaena cambodiana Pierre ex Gagnep. Their chemical structures were elucidated to be (23R,25R)‐26‐O‐β‐D‐glucopyranosyl‐16,23‐cyclocholesta‐5,17(20)‐dien‐22‐one‐3β,16α,26‐triol‐3‐O‐α‐L‐rhamnopyranosyl‐(1→2)‐[α‐L‐rhamnopyranosyl‐(1→3)]‐β‐D‐glucopyranoside (1), (23R,25R)‐26‐O‐β‐D‐glucopyranosyl‐16,23‐cyclocholesta‐5,17,20(22)‐trien‐3β,22,26‐triol‐3‐O‐α‐L‐rhamnopyranosyl‐(1→3)‐β‐D‐glucopyranoside (2), (23R,25R)‐16,23‐cyclocholesta‐5,16,20(22)‐trien‐3β,22,26‐triol‐3‐O‐α‐L‐rhamnopyranosyl‐(1→3)‐β‐D‐glucopyranoside (3), 3β‐[(O‐α‐L‐rhamnopyranosyl‐(1→3)‐[α‐L‐rhamnopyranosyl‐(1→2)]‐β‐D‐gluco‐pyranosyl)oxy]‐pregna‐5,17(20)‐diene‐16‐one‐20‐carboxylic acid 4′′′′‐O‐β‐D‐glucopyranosylisopentyl ester (4), cambodianoside A (5), diosbulbiside C (6), and diosbulbiside D (7), by IR, HR‐ESI‐MS, 1D and 2D NMR spectra. Compounds 1 and 4–7 inhibited nitric oxide (NO) production in lipopolysaccharide activated RAW 264.7 cells with IC50 values ranging from 19.03±1.84 to 67.92±3.81 μM, whereas compounds 2 and 3 were inactive with IC50 values over 100 μM.
Identification of glycosylated nucleosides in small synthetic glyco‐RNAs
Authors: Michael Frank St. , Hamouda Maha Ben , Stupak Jacek , Li Jianjun , Pearson Angela , Sauvageau Janelle
Published: December 2023

Recently, the post‐transcriptional modification of RNA with N‐glycans was reported, changing the paradigm that RNAs are not commonly N‐glycosylated. Moreover, glycan modifications of RNA are investigated for therapeutic targeting purposes. But the glyco‐RNA field is in its infancy with many challenges to overcome. One question is how to accurately characterize glycosylated RNA constructs. Thus, we generated glycosylated forms of Y5 RNA mimics, a short non‐coding RNA. The simple glycans lactose and sialyllactose were attached to the RNA backbone using azide‐alkyne cycloadditions. Using nuclease digestion followed by LC−MS, we confirmed the presence of the glycosylated nucleosides, and characterized the chemical linkage. Next, we probed if glycosylation would affect the cellular response to Y5 RNA. We treated human foreskin fibroblasts in culture with the generated compounds. Key transcripts in the innate immune response were quantified by RT‐qPCR. We found that under our experimental conditions, exposure of cells to the Y5 RNA did not trigger an interferon response, and glycosylation of this RNA did not have an impact. Thus, we have identified a successful approach to chemically characterize synthetic glyco‐RNAs, which will be critical for further studies to elucidate how the presence of complex glycans on RNA affects the cellular response.
Intranodal lymphangiography with lipiodol as a diagnostic and therapeutic approach for spontaneous cervical chyle leak
Authors: Sasaki Yuki , Sakuhara Yusuke , Sasaki Satoru , Maeda Taku , Yamamoto Yuhei , Ishikawa Kosuke
Published: December 2023

Key Clinical Message

We present a case of spontaneous cervical chyle leak that showed as left‐sided neck swelling. Spontaneous chyle leak is extremely rare. Lymphangiography with lipiodol is useful as a diagnostic and therapeutic approach for chyle leak.
Insights into the Structural Evolution Process of Na/ZnFe2O4 Spinel Catalyst in CO2 Hydrogenation
Authors: Gong Xiaoqian , Liu Yi , He Ruonan , Xu Xiaoying , Han Zhihua , Chen Jingyun , Feng Bo , Wang Zhou‐jun , Xing Aihua
Published: December 2023

The CO2 hydrogenation to olefins process over Fe‐based catalysts offer a promising route for the production of high‐value chemicals from non‐fossil route. Herein, we present a Na promoted ZnFe2O4 spinel catalyst and their structural evolution from fresh state to reduction and to reaction period was elucidated. The clear phase segregation between Fe and Zn occurred after reduction/reaction because of crystalline phase transformation in the order of ZnFe2O4→ZnO+Fe7C3+χ‐Fe5C2→FeO+ZnO+Fe7C3+χ‐Fe5C2. The formation of iron carbide phases (Fe7C3 and χ‐Fe5C2) was enhanced dramatically by Na promoter. The adjacent Na promoter increase the electron density in Fe−Zn interfaces and enhance its ability to dissociate CO* to form adsorbed CHx* species, thus promoting the formation of olefins. This Na promoted rich electronic Fe−Zn interfaces alters the balance between iron oxides and iron carbides on the catalyst surface, which accelerate the chain growth reaction and facilitate the coupling efficiency of tandem reaction. The various catalysts were characterized by N2 physisorption, SEM, HR‐TEM, HAADF‐STEM, ex‐situ /in situ XRD, Mössbauer spectra, ICP, in situ XPS, and operando DRIFTs.
Tuning Strong Metal‐Support Interactions for Enhancing Direct Deoxygenation of Biomass‐Lignin Derived Phenolics
Authors: Ding Shining , Zhu Xinli
Published: December 2023

Catalytic direct deoxygenation (DDO) of phenolic compounds to aromatics is an appealing approach for utilization of biomass‐lignin with minimal amount of H2 consumption. Metal/reducible metal oxide catalysts provide two functionalities, i. e., C−H bond formation (hydrogenation) and C−O bond breakage (deoxygenation), required for this reaction that takes place at the interfacial perimeter sites. Strong metal‐support interactions (SMSI) can profoundly alter the density and property of such sites. This short review summarized recent advances in tuning SMSI for enhancing DDO of phenolics. The approaches of varying reduction temperature, modulation of crystal facets and crystal phases of metal oxide, and reduction of mixed metal oxide were discussed for the origin for formation of SMSI, the degree of SMSI, and its consequence on the DDO performance. The analysis revealed that intermediate degree of SMSI with maximal density of metal/oxide interfacial perimeter site enhances DDO while minimizing unfavorable side reactions. This short review highlights the concept of tuning the interfacial perimeter sites via SMSI for reactions which require multiple functionalities and take place at the metal/oxide interface.
School counseling practices related to postsecondary STEM participation
Authors: Gearns Richard , Kelly Angela M. , Bugallo Mónica F.
Published: December 2023

This qualitative exploratory cross‐case analysis analyzed the beliefs and practices of high school counselors related to science, technology, engineering, and mathematics (STEM) academic advisement, postsecondary planning, and career participation. Interviews were conducted with high school counselors (N = 13) who were purposively sampled to represent a diversity of schools in terms of demographic variables. Findings indicated that high school counselors perceived that (a) sociocultural factors influenced student preparation for STEM, career planning, and decision making; (b) students’ STEM‐related career goals and academic behaviors were sometimes misaligned, and academic advisement often mediated this tension; and (c) their professional STEM knowledge, beliefs, and practices were influenced by professional preparation, workplace characteristics, and their academic experiences. Implications include the need for early, sustained high school STEM counseling and academic advisement; accessible professional development in STEM preparation and careers to promote multiple pathways and reduce school counselor bias; and encouraging family involvement in STEM career decision making.
A Review of the Recent Advances in Development of Noble Metal‐Free Materials as Electrocatalysts for Hydrogen and Oxygen Evolution Reactions
Authors: Farajzadeh Mustafa , Rahsepar Fatemeh Rahnemaye
Published: December 2023

Sustainable energy development can no longer be met by fossil fuels alone. Hence, electrochemical water splitting containing oxygen and hydrogen evolution reactions is appealing as a clean energy pathway. As respects the water splitting efficiency which is largely determined by the selectivity, durability, and intrinsic activity of the electrocatalysts, one of the most challenging questions when studying these materials is “which category of electrocatalysts will show the best performance in this issue?” The best electrocatalysts for water splitting still come from noble metals. Although these materials show particularly good efficiency, but due to the scarce resources their massive use is limited. Therefore, the noble metal‐free materials due to their stability, efficiency, abundance and variety of reaction sites were introduced as an interesting candidate for electrochemical water splitting reactions. In this review, based on the important above‐mentioned points, our attention was focused on key categories based on transition metals (TMs), metal organic framework derived (MOF‐derived), carbon‐based hybrids, graphitic carbon nitride (g‐C3N4) hybrids, and bio‐assisted electrocatalysts. These compounds have shown significant activity and stability for broad electrocatalysis applications in water splitting reactions and displaying remarkable potential to replace with noble metal‐based catalysts. This comprehensive review identifies rational strategies for designing and synthesizing high‐performance novel noble metal‐free electrocatalysts for water splitting.
Organometallic Bridge Diversification of Bicyclo[1.1.1]pentanes
Authors: Anderson Joseph M. , Poole Darren L. , Cook Gemma C. , Murphy John A. , Measom Nicholas D.
Published: December 2023

Bicyclo[1.1.1]pentane (BCP) derivatives have attracted significant recent interest in drug discovery as alkyne, tert‐butyl and arene bioisosteres, where their incorporation is frequently associated with increased compound solubility and metabolic stability. While strategies for functionalisation of the bridgehead (1,3) positions are extensively developed, platforms allowing divergent substitution at the bridge (2,4,5) positions remain limited. Recent reports have introduced 1‐electron strategies for arylation and incorporation of a small range of other substituents, but are limited in terms of scope, yields or practical complexity. Herein, we show the synthesis of diverse 1,2,3‐trifunctionalised BCPs through lithium‐halogen exchange of a readily accessible BCP bromide. When coupled with medicinally relevant product derivatisations, our developed 2‐electron “late stage” approach provides rapid and straightforward access to unprecedented BCP structural diversity (>20 hitherto‐unknown motifs reported). Additionally, we describe a method for the synthesis of enantioenriched “chiral‐at‐BCP” bicyclo[1.1.1]pentanes through a novel stereoselective bridgehead desymmetrisation.
A green approach for cohesive recycling and regeneration of electrode active materials from spent lithium‐ion batteries
Authors: Vinayak Anil Kumar , Wang Xiaolei
Published: December 2023

The implementation of the green energy transition by reducing reliance on fossil fuels has fueled the burgeoning demand for lithium‐ion batteries in grid‐level energy storage systems and electric vehicles. The growth of portable electronic devices has also contributed to this exponential demand, creating both logistical and environmental challenges in the supply of raw materials such as lithium and the management of end‐of‐life batteries. Current recycling methods for spent batteries are both energy‐intensive and inefficient. To address these issues, a green approach using organic acid mixtures has been proposed to reclaim lithium from spent cathodes and recover and purify graphite from spent anodes, while also regenerating its structure. The effectiveness of this method is demonstrated through the use of organic acid mixtures to leach and reclaim lithium from NCM 622 batteries. On the anode side, a curing–leaching strategy using organic acids is employed to purify spent graphite, which is subsequently calcined to enhance its interlayer structure conducive to better intercalation of Li+ and improve electrochemical performance. Additionally, recovered graphite is tailored with carbon using water bath carbonization to repair structural defects caused by lithium intercalation and improve electrochemical performance while augmenting the regenerated graphite's quality, equipping it to be reused in batteries or upcycled applications.
Controlling Three‐Step and Five‐Step Spin Transitions by Polymorphism in an FeIII Spin Crossover Complex
Authors: Wu Yingying , Peng Shuang , Zhang Ziyi , Gao Yue , Xu Guangyan , Dai Jingwei , Li Zhao‐Yang , Yamashita Masahiro
Published: December 2023

Comprehensive Summary

Regulating spin crossover (SCO) behavior, especially controlling the spin transition steps, is an important scientific issue, mainly because people aim to control spin bistability and multistability. Presently, SCO bistability can be regulated by changing the ligand‐modifying species, non‐coordinated anions, guest molecules, and metal‐ion dopant. However, the control of multistability is extremely challenging, especially in Fe(III) SCO compounds. Here, we report that [FeIII(H‐5‐Br‐thsa)(5‐Br‐thsa)]·H2O (5‐Br‐thsa = (5‐bromo‐2‐hydroxybenzylidene)hydrazinecarbothioamide), a compound we have reported before, exists in two polymorphic forms: polymorph 1 exhibits three‐step SCO, and polymorph 2 shows five‐step SCO, with multi‐step SCO behavior effectively regulated by polymorphism. According to single‐crystal and powder X‐ray diffractometry, polymorphs 1 and 2 crystallize in different space groups during their spin transitions, with two‐step symmetry breaking observed (Pbcn → Pnc2 → Pbcn for polymorph 1; P21/n → Pn → P21/n for polymorph 2). We realized that the behavior of these two polymorphs depends significantly on the structure, including (i) the average Fe—N bond distance, (ii) deformation of octahedral FeIII atoms, and (iii) distinct crystal packing, which account for the large differences observed in magnetic properties.
Satisfaction with care, general health, and mental health among sexual and gender minority cancer survivors: Results of the OUT National Cancer Survey
Authors: Kamen Charles S. , Gada Umang , Lyerly Reece , Scout N. F. N.
Published: December 2023

Background

Few studies have attempted to characterize the cancer care experiences and outcomes of sexual and gender minority (SGM) patients with cancer, despite indications that this population experiences disparities across the cancer continuum. The current study used descriptive and exploratory methods to assess factors related to SGM cancer patients’ satisfaction with cancer care and self‐reported physical and mental health.

Methods

The authors designed a cross‐sectional self‐report online survey and recruited 3750 SGM cancer patient participants (mixed cancers; 85.6% White; 57% gay, 24% lesbian, 6.7% bisexual, and 6.2% transgender/gender nonbinary) using social media posts, partner organizations, and paid advertisements. They analyzed data using descriptive approaches and exploratory multivariate logistic regression models.

Results

Overall, 70.6% of participants reported feeling satisfied with the cancer care they received, 70% rated their physical health as very good or excellent, and 46% reported experiencing less than 5 days of poor mental health in the last month. In models including all participants, complete cases, and Black, Indigenous, and people of color (BIPOC), satisfaction with care was consistently associated with receiving treatment in an SGM welcoming environment. Physical health was consistently associated with having strong social support after cancer. Mental health was consistently associated with feeling safe disclosing SGM identities.

Conclusions

SGM cancer patients treated in SGM‐welcoming environments were over six times more likely to be satisfied with the care they received than those treated in nonwelcoming environments; this and other modifiable factors could be the target of further study and intervention.
A Randomized Phase I Study of the Anti‐Interleukin‐33 Antibody Tozorakimab in Healthy Adults and Patients With Chronic Obstructive Pulmonary Disease
Authors: Reid Fred , Singh Dave , Albayaty Muna , Moate Rachel , Jimenez Eulalia , Sadiq Muhammad Waqas , Howe David , Gavala Monica , Killick Helen , Williams Adam , Krishnan Surekha , Godwood Alex , Shukla Animesh , Hewitt Lisa , Lei Alejhandra , Kell Chris , Pandya Hitesh , Newcombe Paul , White Nicholas , Scott Ian C. , Cohen E. Suzanne
Published: December 2023

Tozorakimab is a human monoclonal antibody that neutralizes interleukin (IL)‐33. IL‐33 is a broad‐acting epithelial “alarmin” cytokine upregulated in lung tissue of patients with chronic obstructive pulmonary disease (COPD). This first‐in‐human, phase I, randomized, double‐blind, placebo‐controlled study (NCT03096795) evaluated the safety, tolerability, pharmacokinetics (PKs), immunogenicity, target engagement, and pharmacodynamics (PDs) of tozorakimab. This was a 3‐part study. In part 1, 56 healthy participants with a history of mild atopy received single escalating doses of either intravenous or subcutaneous tozorakimab or placebo. In part 2, 24 patients with mild COPD received multiple ascending doses of subcutaneous tozorakimab or placebo. In part 3, 8 healthy Japanese participants received a single intravenous dose of tozorakimab or placebo. The safety data collected included treatment‐emergent adverse events (TEAEs), vital signs, and clinical laboratory parameters. Biological samples for PKs, immunogenicity, target engagement, and PD biomarker analyses were collected. No meaningful differences in the frequencies of TEAEs were observed between the tozorakimab and placebo arms. Three tozorakimab‐treated participants with COPD experienced treatment‐emergent serious adverse events. Subcutaneous or intravenous tozorakimab demonstrated linear, time‐independent PKs with a mean half‐life of 11.7–17.3 days. Treatment‐emergent anti‐drug antibody frequency was low. Engagement of tozorakimab with endogenous IL‐33 in serum and nasal airways was demonstrated. Tozorakimab significantly reduced serum IL‐5 and IL‐13 levels in patients with COPD compared with placebo. Overall, tozorakimab was well tolerated, with a linear, time‐independent serum PK profile. Additionally, biomarker studies demonstrated proof of mechanism. Overall, these data support the further clinical development of tozorakimab in COPD and other inflammatory diseases.
Population Pharmacokinetic Analysis of Atomoxetine and its Metabolites in Children and Adolescents with Attention‐Deficit/Hyperactivity Disorder
Authors: Cheng Shen , Al‐Kofahi Mahmoud , Leeder J. Steven , Brown Jacob T.
Published: December 2023

Atomoxetine (ATX) is a non‐stimulant used to treat attention‐deficit/hyperactivity disorder (ADHD) and systemic exposure is highly variable due to polymorphic cytochrome P450 2D6 (CYP2D6) activity. The objective of this study was to characterize the time course of ATX and metabolites (4‐hydroxyatomoxetine (4‐OH); N‐desmethylatomoxetine (NDA); and 2‐carboxymethylatomoxetine (2‐COOH)) exposure following oral ATX dosing in children with ADHD to support individualized dosing. A nonlinear mixed‐effect modeling approach was used to analyze ATX, 4‐OH, and NDA plasma and urine, and 2‐COOH urine profiles obtained over 24–72 hours from children with ADHD (n = 23) following a single oral ATX dose. Demographics and CYP2D6 activity score (AS) were evaluated as covariates. Simulations were performed to explore the ATX dosing in subjects with various CYP2D6 AS. A simultaneous pharmacokinetic modeling approach was used in which a model for ATX, 4‐OH, and NDA in plasma and urine, and 2‐COOH in urine was developed. Plasma ATX, 4‐OH, and NDA were modeled using two‐compartment models with first‐order elimination. CYP2D6 AS was a significant determinant of ATX apparent oral clearance (CL/F), fraction metabolized to 4‐OH, and systemic exposure of NDA. CL/F of ATX varied almost 7‐fold across the CYP2D6 AS groups: AS 2: 20.02 L/hour; AS 1: 19.00 L/hour; AS 0.5: 7.47 L/hour; and AS 0: 3.10 L/hour. The developed model closely captures observed ATX, 4‐OH, and NDA plasma and urine, and 2‐COOH urine profiles. Application of the model shows the potential for AS‐based dosing recommendations for improved individualized dosing.
Improvement in left atrial strain following ferric carboxymaltose in heart failure: an analysis of the Myocardial‐IRON trial
Authors: Santas Enrique , del Canto Irene , Cardells Ingrid , Miñana Gema , Llàcer Pau , Almenar Luis , Fácila Lorenzo , Maceira Alicia M. , Sanchis Juan , Núñez Julio ,   Myocardial‐IRON Investigators
Published: December 2023

Aims

Iron deficiency (ID) is associated with an impaired cardiac function and remodelling in heart failure (HF). Treatment with ferric carboxymaltose (FCM) has been showed recently to improve biventricular systolic function and ventricular strain parameters in patients with HF with reduced ejection fraction and ID, but there is no evidence on the benefit of FCM on the left atrium (LA). In this study, we aimed to evaluate the effect of FCM on LA longitudinal strain (LA‐LS).

Methods and results

This is a post hoc subanalysis of a double‐blind, placebo‐controlled, randomized clinical trial that enrolled 53 ambulatory patients with HF, left ventricular ejection fraction (LVEF) < 50%, and ID [Myocardial‐IRON trial (NCT03398681)], treated with FCM or placebo. Cardiac magnetic resonance‐featured tracking (CMR‐FT) strain changes were evaluated before and 7 and 30 days after randomization using linear mixed regression analysis. The median age of the sample was 68 years (interquartile range: 64–76), and 20 (69%) were men. Mean ± standard deviation of LVEF was 39 ± 11%, and most (97%) were in stable New York Heart Association class II. At baseline, mean LA‐LS was −8.9 ± 3.5%. At 30 days, and compared with placebo, LA‐LS significantly improved in those allocated to FCM treatment arm (LA‐LS = −12.0 ± 0.5 and −8.5 ± 0.6, respectively; −
3.55%, P < 0.001).

Conclusions

In patients with stable HF, LVEF < 50%, and ID, treatment with FCM was associated with short‐term improvements in LA‐LS assessed by CMR‐FT. Future works should assess the potential benefit of iron repletion on LA function.
Geriatric Nutritional Risk Index predicts bleeding event in patients with heart failure
Authors: Sato Yu , Yoshihisa Akiomi , Nozaki Yuji , Ohara Himika , Sugawara Yukiko , Abe Satoshi , Misaka Tomofumi , Sato Takamasa , Oikawa Masayoshi , Kobayashi Atsushi , Yamaki Takayoshi , Nakazato Kazuhiko , Takeishi Yasuchika
Published: December 2023

Aims

We aimed to elucidate the association between malnutrition and the occurrence of bleeding events in patients with heart failure.

Methods and results

We evaluated the nutritional status of patients with heart failure [n = 2044, median (inter‐quartile range) age 69.0 (59.0–78.0) years, 1209 (59.1%) males] using the Geriatric Nutritional Risk Index (GNRI). The primary endpoint was a composite of bleeding events such as haemorrhagic stroke or gastrointestinal bleeding. According to the survival classification and regression tree analysis, the accurate cut‐off point of GNRI for predicting the primary endpoint was 106.2. We divided the patients into two groups based on GNRI levels: high GNRI group (GNRI ≥ 106.2, n = 606, 29.6%) and low GNRI group (GNRI < 106.2, n = 1438, 70.4%). We compared the patients' characteristics and prognosis between the two groups. The low GNRI group was older [72.0 (63.0–79.0) vs. 63.0 (53.0–73.0) years, P < 0.001] and had a lower prevalence of male sex (56.9% vs. 64.5%, P = 0.001). There were no differences in the use of antiplatelet agents and anticoagulants between the two groups. Levels of B‐type natriuretic peptide were higher [321.1 (123.3–667.4) vs. 111.6 (42.6–235.4) pg/mL, P < 0.001] and levels of haemoglobin were lower [12.4 (10.8–13.7) vs. 14.2 (12.9–15.4) g/dL, P < 0.001] in the low GNRI group. The Kaplan–Meier analysis demonstrated that bleeding event rates were higher in the low GNRI group (log‐rank P < 0.001). The multivariable Cox proportional hazard analysis revealed that low GNRI (hazard ratio 1.952, 95% confidence interval 1.002–3.805, P = 0.049) was associated with bleeding events.

Conclusions

Heart failure patients with poor nutritional status, determined by GNRI under 106.2, experienced high bleeding event rates. Comprehensive management is required to avoid bleeding event in those populations.
Reaction Pathway for the Aerobic Oxidation of Phosphines Catalyzed by Oxomolybdenum Salen Complexes
Authors: Rusmore Theo A. , Lander Chance , Nicholas Kenneth M.
Published: December 2023

Catalysis of O‐atom transfer (OAT) reactions is a characteristic of both natural (enzymatic) and synthetic molybdenum‐oxo and ‐peroxo complexes. These reactions can employ a variety of terminal oxidants, e. g. DMSO, N‐oxides, and peroxides, etc., but rarely molecular oxygen. Here we demonstrate the ability of a set of Schiff‐base‐MoO2 complexes (cy‐salen)MoO2 (cy‐salen=N,N’‐cyclohexyl‐1,2‐bis‐salicylimine) to catalyze the aerobic oxidation of PPh3. We also report the results of a DFT computational investigation of the catalytic pathway, including the identification of energetically accessible intermediates and transition states, for the aerobic oxidation of PMe3. Starting from the dioxo species, (cy‐salen)Mo(VI)O2 (1), key reaction steps include: 1) associative addition of PMe3 to an oxo‐O to give LMo(IV)(O)(OPMe3) (2); 2) OPMe3 dissociation from 2 to produce mono‐oxo complex (cy‐salen)Mo(IV)O (3); 3) stepwise O2 association with 3 via superoxo species (cy‐salen)Mo(V)(O)(η1‐O2) (4) to form the oxo‐peroxo intermediate (cy‐salen)Mo(VI)(O)(η2‐O2) (5); 4) the O‐transfer reaction of PMe3 with oxo‐peroxo species 5 at the oxo‐group, rather than the peroxo unit leading, after OPMe3 dissociation, to a monoperoxo species, (cy‐salen)Mo(IV)(η2‐O2) (7); and 5) regeneration of the dioxo complex (cy‐salen)Mo(VI)O2 (1) from the monoperoxo triplet 37 or singlet 17 by a concerted, asynchronous electronic isomerization. An alternative pathway for recycling of the oxo‐peroxo species 5 to the dioxo‐Mo 1 via a bimetallic peroxo complex LMo(O)‐O−O‐Mo(O)L 8 is determined to be energetically viable, but is unlikely to be competitive with the primary pathway for aerobic phosphine oxidation catalyzed by 1.
AoI‐driven SWIPT‐enabled UAV trajectory optimization for two‐way relaying
Authors: Perera Tharindu D. Ponnimbaduge , Jayakody Dushantha Nalin K.
Published: December 2023

Motivated by the timely need for fresh updates in time‐critical applications, this paper investigates the AoI‐driven UAV trajectory optimization for a two‐way relay network. The non‐linear simultaneous wireless information and power transfer (SWIPT) power‐splitting (PS) technique is used to provide the energy required for UAV communication considering hardware impairments. Amalgamating derived outage probability, AoI expression is obtained to evaluate data timeliness and its performance trade‐offs. Then, we optimize the trajectory of the UAV while minimizing the AoI performance within the given discretized time slot. The impact of the system parameters, that is, size of the status update, PS factor, outage probability, and UAV's position, on the AoI performance are extensively investigated.