bluuebunny/crossref_metadata_2025 huggingface dataset:
Tunable Narrow‐Band Cyan‐Emission of Eu2+‐doped Nitridomagnesophosphates Ba3−xSrx[Mg2P10N20] : Eu2+ (x=0–3)
Authors: Pritzl Reinhard M. , Pointner Monika M. , Witthaut Kristian , Strobel Philipp , Schmidt Peter J. , Schnick Wolfgang
Published: April 2024

Tetrahedron‐based nitrides offer a wide range of properties and applications. Highly condensed nitridophosphates are examples of nitrides that exhibit fascinating luminescence properties when doped with Eu2+, making them appealing for industrial applications. Here, we present the first nitridomagnesophosphate solid solution series Ba3−xSrx[Mg2P10N20] : Eu2+ (x=0–3), synthesized by a high‐pressure high‐temperature approach using the multianvil technique (3 GPa, 1400 °C). Starting from the binary nitrides P3N5 and Mg3N2 and the respective alkaline earth azides, we incorporate Mg into the P/N framework to increase the degree of condensation κ to 0.6, the highest observed value for alkaline earth nitridophosphates. The crystal structure was elucidated by single‐crystal X‐ray diffraction, powder X‐ray diffraction, energy‐dispersive X‐ray spectroscopy (EDX), and solid‐state NMR. DFT calculations were performed on the title compounds and other related highly condensed nitridophosphates to investigate the influence of Mg in the P/N network. Eu2+‐doped samples of the solid solution series show a tunable narrow‐band emission from cyan to green (492–515 nm), which is attributed to the preferred doping of a single crystallographic site. Experimental confirmation of this assumption was provided by overdoping experiments and STEM‐HAADF studies on the series as well on the stoichiometric compound Ba2Eu[Mg2P10N20] with additional atomic resolution energy‐dispersive X‐ray spectroscopy (EDX) mapping.
Cage‐To‐Cage Transformations in Self‐Assembled Coordination Cages Using “Acid/Base” or “Guest Binding‐Induced Strain” as Stimuli
Authors: Sivalingam Vellaiyadevan , Parbin Minaz , Krishnaswamy Shobhana , Chand Dillip Kumar
Published: April 2024

Controlling supramolecular systems between different functional forms by utilizing acids/bases as stimuli is a formidable challenge, especially where labile coordination bonds are involved. A pair of acid/base responsive, interconvertible 1,5‐enedione/pyrylium based Pd2L4‐type cages are prepared that exhibit differential guest binding abilities towards disulfonates of varied sizes. A three‐state switch has been achieved, where (i) a weakly coordinating base induced cage‐to‐cage transformation in the first step, (ii) a strongly coordinating base triggered cage disassembly as the second step, and (iii) the third step shows acid(strong) promoted generation of initial cage, thereby completing the cycle. To our surprise, binding of a specific disulfonate guest facilitated cage‐to‐cage transformations by inducing strain on the cage assembly thereby opening the labile pyrylium rings of the cage. Through a competitive guest binding study, we demonstrated the superior guest binding capability of the octacationic pyrylium‐based cage over a similar‐sized tetracationic cage. These results provide a reliable approach to reversibly modulate the guest binding properties of acid/base‐responsive self‐assembled coordination cages.
Unveiling Low Temperature Assembly of Dense Fe‐N4 Active Sites via Hydrogenation in Advanced Oxygen Reduction Catalysts
Authors: Yin Shuhu , Li Yanrong , Yang Jian , Liu Jia , Yang Shuangli , Cheng Xiaoyang , Huang Huan , Huang Rui , Wang Chong‐Tai , Jiang Yanxia , Sun Shigang
Published: April 2024

The single‐atom Fe−N−C is a prominent material with exceptional reactivity in areas of sustainable energy and catalysis research. It is challenging to obtain the dense Fe‐N4 site without the Fe nanoparticles (NPs) sintering during the Fe−N−C synthesis via high‐temperature pyrolysis. Thus, a novel approach is devised for the Fe−N−C synthesis at low temperatures. Taking FeCl2 as Fe source, a hydrogen environment can facilitate oxygen removal and dichlorination processes in the synthesis, efficiently favouring Fe‐N4 site formation without Fe NPs clustering at as low as 360 °C. We shed light on the reaction mechanism about hydrogen promoting Fe‐N4 formation in the synthesis. By adjusting the temperature and duration, the Fe‐N4 structural evolution and site density can be precisely tuned to directly influence the catalytic behaviour of the Fe−N−C material. The FeNC‐H2‐360 catalyst demonstrates a remarkable Fe dispersion (8.3 wt %) and superior acid ORR activity with a half‐wave potential of 0.85 V and a peak power density of 1.21 W cm−2 in fuel cell. This method also generally facilitates the synthesis of various high‐performance M−N−C materials (M=Fe, Co, Mn, Ni, Zn, Ru) with elevated single‐atom loadings.
Helicene Aromaticity Deviates from the Clar Rule—On the Electronic Dissimilarity of Large Isomeric Fibonacenes
Authors: Sturm Ludmilla , Artigas Albert , Coquerel Yoann , Bechtold Ivan H. , Durola Fabien , Bock Harald
Published: April 2024

This combined experimental and theoretical study illustrates the profound consequences of non‐planarity on the electronic properties of polycyclic arenes. Three isomeric [10]fibonacene tetraesters were synthesized through a robust and regiocontrolled Perkin/Mallory approach: a nearly planar [10]phenacene derivative, a moderately twisted [10]semicircle derivative, and a 3D non‐planar [10]helicene derivative. The photophysical properties of the 3D [10]helicene isomer were found to be dramatically different from the comparable ones of the [10]phenacene and [10]semicircle isomers. The aromatic properties of the [10]phenacene and [10]semicircle isomers conform well with their predictive Kekulé and Clar analyses, but the [10]helicene isomer deviates from these general topological rules, which appears to be a general phenomenon for [n]fibonacenes with n≥9.
Pyridine‐Based Covalent Organic Frameworks with Pyridyl‐Imine Structures for Boosting Photocatalytic H2O2 Production via One‐Step 2e− Oxygen Reduction
Authors: Wu Weijian , Li Zixuan , Liu Shiyin , Zhang Di , Cai Bingzi , Liang Yizhao , Wu Mingxing , Liao Yaozu , Zhao Xiaojia
Published: April 2024

Bipyridine‐based covalent organic frameworks (COFs) have emerged as promising contenders for the photocatalytic generation of hydrogen peroxide (H2O2). However, the presence of imine nitrogen alters the mode of H2O2 generation from an efficient one‐step two‐electron (2e−) route to a two‐step 2e− oxygen reduction pathway. In this work, we introduce 3,3′‐bipyridine units into imine‐based COF skeletons, creating a pyridyl‐imine structure with two adjacent nitrogen atoms between the pyridine ring and imine linkage. This unique bipyridine‐like architecture can effectively suppress the two‐step 2e− ORR process at the single imine‐nitrogen site, facilitating a more efficient one‐step 2e− pathway. Consequently, the optimized pyridyl‐imine COF (PyIm‐COF) exhibits a remarkable H2O2 production rate of up to 5850 μmol h−1 g−1, nearly double that of pristine bipyridine COFs. This work provides valuable insight into the rational design of functionalized COFs for enhanced H2O2 production in photocatalysis.
Additive Manufacturing of Micro‐Architected Copper based on an Ion‐Exchangeable Hydrogel
Authors: Ma Songhua , Bai Wuxin , Xiong Dajun , Shan Guibin , Zhao Zijie , Yi Wenbin , Wang Jieping
Published: April 2024

Additive manufacturing (AM) of copper through laser‐based processes poses challenges, primarily attributed to the high thermal conductivity and low laser absorptivity of copper powder or wire as the feedstock. Although the use of copper salts in vat photopolymerization‐based AM techniques has garnered recent attention, achieving micro‐architected copper with high conductivity and density has remained elusive. In this study, we present a facile and efficient process to create complex 3D micro‐architected copper structures with superior electrical conductivity and hardness. The process entails the formulation of an ion‐exchangeable photoresin, followed by the utilization of digital light processing (DLP) printing to sculpt 3D hydrogel scaffolds, which were transformed into Cu2+‐chelated polymer frameworks (Cu‐CPFs) with a high loading of Cu2+ ions through ion exchange, followed by debinding and sintering, results in the transformation of Cu‐CPFs into miniaturized copper architectures. This methodology represents an efficient pathway for the creation of intricate micro‐architected 3D metal structures.
Palladium‐Catalyzed C3‐Carbaldehyde Directed Regioselective C2‐Thioarylation of Indoles
Authors: Kumar Gupta Sandip , Panda Niranjan
Published: April 2024

Palladium‐catalyzed thioarylation of indoles by diaryl disulfides in the presence of phenyliododiacetate is reported. The directing potential of weakly coordinating aldehyde group present at 3‐position of indole was exploited for regioselective C2‐H thioarylation over the possible C4‐H functionalization. Mechanistic studies reveal that the process involves initial generation of thioaryl radical followed by sequential C−H activation, thiolate transfer, and reductive elimination.
Characterization and engineering of peroxisome targeting sequences for compartmentalization engineering in Pichia pastoris
Authors: Ye Cuifang , Hong Haosen , Gao Jucan , Li Mengxin , Gou Yuanwei , Gao Di , Dong Chang , Huang Lei , Xu Zhinan , Lian Jiazhang
Published: April 2024

Peroxisomal compartmentalization has emerged as a highly promising strategy for reconstituting intricate metabolic pathways. In recent years, significant progress has been made in the peroxisomes through harnessing precursor pools, circumventing metabolic crosstalk, and minimizing the cytotoxicity of exogenous pathways. However, it is important to note that in methylotrophic yeasts (e.g. Pichia pastoris), the abundance and protein composition of peroxisomes are highly variable, particularly when peroxisome proliferation is induced by specific carbon sources. The intricate subcellular localization of native proteins, the variability of peroxisomal metabolic pathways, and the lack of systematic characterization of peroxisome targeting signals have limited the applications of peroxisomal compartmentalization in P. pastoris. Accordingly, this study established a high‐throughput screening method based on β‐carotene biosynthetic pathway to evaluate the targeting efficiency of PTS1s (Peroxisome Targeting Signal Type 1) in P. pastoris. First, 25 putative endogenous PTS1s were characterized and 3 PTS1s with high targeting efficiency were identified. Then, directed evolution of PTS1s was performed by constructing two PTS1 mutant libraries, and a total of 51 PTS1s (29 classical and 22 noncanonical PTS1s) with presumably higher peroxisomal targeting efficiency were identified, part of which were further characterized via confocal microscope. Finally, the newly identified PTS1s were employed for peroxisomal compartmentalization of the geraniol biosynthetic pathway, resulting in more than 30% increase in the titer of monoterpene compared with when the pathway was localized to the cytosol. The present study expands the synthetic biology toolkit and lays a solid foundation for peroxisomal compartmentalization in P. pastoris.
Prevalence of attention‐deficit hyperactivity disorder in adult prisoners: An updated meta‐analysis
Authors: Fazel Seena , Favril Louis
Published: April 2024

Background

Previous meta‐analyses may have overestimated the prevalence of attention‐deficit hyperactivity disorder (ADHD) in prisoners by including data from selected samples.

Aims

To estimate the prevalence of ADHD in unselected samples of adults in prison and examine potential sources of heterogeneity by meta‐regression and subgroup analyses.

Methods

We assessed all studies included in a 2018 systematic review for eligibility and updated the literature search to include studies published up to September 2023.

Results

A total of 11 studies reporting robust diagnostic data on ADHD in 3919 unselected adults in prison were included. In meta‐regression, ADHD prevalence did not differ between men and women but it was significantly higher in studies using a two‐phase design. In random sampling studies, the pooled prevalence of ADHD was 8.3% (95% CI: 3.8–12.8) which was further halved after the removal of an outlier.

Conclusion

One in 12 adults in prison have been diagnosed with ADHD. Our findings highlight the importance of using clear and consistent inclusion criteria in meta‐analyses of prevalence.
Solid state, pulsed‐wave 355 nm UV laser atherectomy debulking in the treatment of infrainguinal peripheral arterial disease: The Pathfinder Registry
Authors: Das Tony S. , Shammas Nicolas W. , Yoho Jason A. , Martinez‐Clark Pedro , Ramaiah Venkatesh , Leon Luis R. , Pacanowski John P. , Tai Zaheed , Ali Vaqar , Arslan Bulent , Rundback John
Published: April 2024

Background

Atherectomy is an important option for debulking atherosclerotic plaque from diseased arteries in patients with infrainguinal arterial disease. Laser atherectomy uses a high‐powered laser to remove the plaque from the arteries to restore blood flow.

Aims

The Pathfinder multicenter registry was initiated to evaluate the safety and efficacy of the 355 nm laser atherectomy system in a real‐world setting for the treatment of de novo, re‐stenotic and in‐stent restenosis (ISR) lesions in infrainguinal arteries of patients with peripheral artery disease (PAD).

Methods

The study was a prospective, single‐arm, multicenter, open‐label registry study for patients treated with the 355 nm laser system. Clinical and lesion characteristics, procedural safety and efficacy data, and baseline, 6‐, and 12‐month outcomes data, including Ankle Brachial Index (ABI), Rutherford class, and Walking Impairment Questionnaires (WIQ), were collected. The primary efficacy endpoint was the achievement of ≤30% final residual stenosis at the index lesion postatherectomy and adjunctive therapy evaluated by an angiographic Core Lab. The primary safety endpoint was the percentage of subjects who did not experience periprocedural major adverse events (PPMAEs) before discharge.

Results

One hundred and two subjects with 121 lesions treated with the 355 nm laser device at 10 centers were included in the analysis. Mean age was 68.4 ± 10.21 years, 61.8% of subjects were male, 44.6% had critical limb ischemia (CLI), and 47.3% had tibial lesions. The mean residual stenosis at the end of the procedure was 24.4 ± 15.5 with 69 lesions (69.0%) achieving technical procedural success (<30% stenosis); similar rates were observed for subjects with ISR (25.5 ± 14.9), chronic total occlusion (CTO) (28.1 ± 17.0), and severe calcification (36.5 ± 21.6) lesions. Mean ABI, Rutherford, and WIQ scores were improved at both 6 and 12 months. Ninety‐seven of 102 subjects (95.1%) met the primary safety endpoint of not experiencing a PPMAE before discharge.

Conclusions

The initial data from the Pathfinder Registry demonstrates the 355 nm laser system is safe and effective in a real‐world setting for performing atherectomy in patients with infrainguinal PAD.
Extent of cardiac damage before transcatheter aortic valve replacement: Beyond aortic stenosis per se
Authors: Kornowski Ran
Published: April 2024

Key points

The cardiac damage classification characterized the extent of cardiac pathology associated with AS before AVR.

Such classification has important prognostic implications for clinical outcomes and repeat HF or CV hospitalizations after TAVR.

Adjunctive cardiac pathology could extend beyond AS per se, which makes it a wide‐ranging syndrome with diverse prognostic and therapeutic implications.
Incorporation of intermediate wheatgrass (Thinopyrum intermedium) into bread wheat doughs: Effects on pasting and rheological properties
Authors: Trevisan Susane , Koksel Filiz , Cetiner Buket , Shamanin Vladimir P. , Pototskaya Inna V. , Ozdemir Bayram , Morgounov Alexey I. , Koksel Hamit
Published: April 2024

Background and Objectives

Intermediate wheatgrass (IWG), a resilient perennial grain with adaptability to difficult climates, is emerging as a compelling candidate for sustainable food solutions in bakery product applications. This study evaluated the pasting and rheological properties of doughs made from bread wheat flour and blended bread wheat–IWG flours (IWG content: 15%, 30%, 45% and 60%), with the goal of exploring the potential of IWG flour as a nutritious and sustainable ingredient in cereal‐based products.

Findings

The RVA peak, trough, and final viscosity values significantly (p < .05) decreased, and the pasting temperature increased as the IWG substitution level increased. IWG‐containing flour blends had a lower retrogradation tendency compared to the control. As the IWG flour substitution level increased, both empirical (Mixograph, Kieffer dough and gluten extensibility, Glutograph) and fundamental (linear oscillatory frequency sweep and creep–recovery) rheological measurements indicated relatively weaker dough properties imparted by the addition of the IWG flour.

Conclusions

The outcomes of this research will shed light on the impacts of utilizing alternative grains, such as intermediate wheatgrass, in bakery applications. This will provide insights that could inform the development of nutritious and sustainable baked products to meet the demands of health‐conscious consumers.

Significance and Novelty

The dough weakening effect of the IWG flour was tolerated at the 15% IWG flour substitution level. At lower substitution levels, the IWG‐containing flour blends exhibited a lower retrogradation tendency compared to bread wheat flour, which could indicate lower staling of loaves of bread during bread storage without compromising the physical quality of bakery products. Finally, the present research fills a critical gap in the literature as it represents the first application of fundamental rheological methods at known and controlled strain and stresses to evaluate the physical properties of doughs prepared from IWG flour blends.
A Versatile Electrochemical Cell for Operando XAS
Authors: Ostervold Lars , Hoffman Adam S. , Thompson David , Bare Simon R. , Clark Ezra Lee
Published: April 2024

In situ and operando X‐ray absorption spectroscopy (XAS) provides fundamental insight into the working principles of electrocatalysts and is an important tool for future catalyst development. However, the design of an operando XAS electrocatalytic cell is not facile, and researchers designing cells, whether new cells or modifications to previous cells, often spend many hours on cell design before obtaining high‐quality XAS data. Here, we describe the design, with engineering drawings, and operation of a versatile XAS cell with options for gas flow, electrolyte flow, pH monitoring, temperature monitoring, and the ability to handle many catalyst forms (any catalyst that can be deposited onto a conductive X‐ray transparent substrate). We benchmarked XAS spectra collected using the new experimental cell to a previous cell design showing its ability to produce quality XAS data. We demonstrate the viability of this cell by providing insight into electrocatalysts by studying cation effects and show the tetrabutylammonium cation prevents bulk oxidation of copper. We hope the availability of this cell allows researchers to convert time typically spent on cell design to time spent on breakthroughs in electrocatalysis.
Synthesis, Characterization and Reactivity Studies of Cobalt(III) Porphyrin‐Iodosylarene Adduct and Cobalt(III) Porphyrin π‐Cation Radical Species
Authors: Fu Wenwen , Wang Shoujun , Zhang Yuheng , Xu Minghao , Sun Dongru , Nam Wonwoo , Wang Yong , Guo Mian
Published: April 2024

Biomimetic metalloporphyrin complexes have been employed in a number of catalytic oxidation reactions by utilizing terminal oxidants such as iodosylarenes (ArIO). Although high‐valent metal‐oxo species have been considered as the reactive intermediates, their precursors, metal‐iodosylarene adduct species, also exhibit intriguing oxidation capability under certain conditions. However, late transition metal porphyrin‐oxidant adduct species have not been explored in oxidation reactions yet. Herein, we report the synthesis, characterization and reactivity studies of cobalt(III) porphyrin‐ArIO adduct complexes. These adduct species exhibit moderate oxidation capability in electron transfer reactions. More interestingly, addition of Brønsted acid or Lewis acid facilitated the O−I bond cleavage, resulted in the formation of cobalt(III) porphyrin π‐cation radical species, which is much more reactive than the corresponding adduct species in electron transfer reactions. Kinetic studies and theoretical calculations demonstrate that the O−I bond cleavage is triggered in the presence of acid, affording the porphyrin ligand oxidation while the formation of high‐valent cobalt‐oxo species is prohibited due to the “oxo‐wall” for late transition metals. This study provides a novel model of a late transition metal‐iodosylarene adduct species as an active oxidant in oxidation reactions, while in the cases of iron and manganese complexes, high‐valent metal‐oxo species are generated.
Magnetically Reusable Carbon Nanotube Coated Co‐based Catalysts towards Highly Efficient Transfer Hydrogenation of Nitroarenes
Authors: Ma Zongyan , Chen Jing , Chen Ming , Dong Linkun , Mao Weiwen , Long Yu , Ma Jiantai
Published: April 2024

Development of efficient and stable non‐noble metal catalysts applied to the catalytic transfer hydrogenation of nitroarenes under mild conditions is still challenging. Herein, we report magnetically recyclable catalysts prepared via simple two‐stage pyrolysis of Co‐MOF‐74 and melamine composites. The optimized catalyst Co@C/CNTs‐10‐700 shows excellent conversion and selectivity towards transfer hydrogenation of nitroarenes with different hydrogen donors. Its excellent stability against formic acid corrosion makes it can be used in a wide range. The excellent catalytic performance can be ascribed to the synergistic effect between carbon nanotubes and Co nanoparticles. Furthermore, the catalyst was easily recycled owing to its magnetism and reused up to ten consecutive cycles without significant loss of activity, indicating that the excellent catalytic stability holds great promise in fields of industrial application.
Catalytic Asymmetric Approach to 1,3,4,5‐Tetrahydro‐1,4‐benzodiazepin‐2‐ones in One‐Pot
Authors: Battaglia Vincenzo , Meninno Sara , Astone Armando , Lattanzi Alessandra
Published: April 2024

Herein we illustrate a first asymmetric synthesis of medicinally attractive tetrahydro‐1,4‐benzodiazepin‐2‐ones performed under catalytic conditions and one‐pot fashion. The process relies on a sequential Knoevenagel reaction/asymmetric epoxidation/domino ring‐opening cyclization (DROC) using commercially available aldehydes, phenylsulfonylacetonitrile, cumyl hydroperoxide, 2‐(aminomethyl)aniline and a readily available quinine‐derived urea as the catalyst. The heterocycles have been isolated with good regioselectivity, satisfactory to good yield and up to 98 % ee. The protocol proved also to be suitable for the preparation of previously undescribed 1,5‐dihydro‐4,1‐benzoxazepin‐3(2H)‐ones with up to 86 % ee.
Metal Free Functionalization of Saturated Heterocycles with Vinylarenes and Pyridine Enabled by Photocatalytic Hydrogen Atom Transfer
Authors: Xu Junhua , Liu Bin
Published: April 2024

Saturated heterocycles are important class of structural scaffolds in small‐molecule drugs, natural products, and synthetic intermediates. Here, we disclosed a metal free, mild, and scalable functionalization of saturated heterocycles using vinylarenes as a linchpin approach. Key to success of this transformation is the employing of simple and cheap benzophenone as a hydrogen atom transfer (HAT) catalyst. This operationally robust process was used for the making of diverse functionalized saturated heterocycles. Furthermore, aldehydes, alkane, and alcohol have been functionalized under the optimized conditions. The potential pharmaceutical utility of the procedure has also been demonstrated by late‐stage functionalization of bioactive natural compounds and pharmaceutical molecules. Initial mechanism studies and control experiments were performed to elucidate the mechanism of the reactions
Synthesis and Lewis Acid Properties of Neutral Silver(III) Adducts Containing the AgIII(CF3)3 Moiety
Authors: Demonti Luca , Joven‐Sancho Daniel , Saffon‐Merceron Nathalie , Baya Miguel , Nebra Noel
Published: April 2024

The acetonitrile AgIII complex [AgIII(CF3)3(NCCH3)] (2) has been reported independently by Eujen and Naumann in the last century, albeit with intriguing NMR discrepancy. In their reports, 2 was claimed to be obtained starting from either [AgIII(CF3)3Cl]− (3⋅Cl) or [AgIII(CF3)4]− (1) via halide abstraction using AgNO3 or acidic treatment, resp. These two synthetic routes are herein reinvestigated. The feasibility of Naumann's method is demonstrated, thus providing 2 yet accompanied by its s‐triazinyl derivative [AgIII(CF3)3(C6H9N3)] (2’). The formation of 2’ is unprecedented and was thereby investigated. Both 2 and 2’ were isolated in pure fashion and fully characterized. In turn, halide extraction from 3⋅Cl leads to the AgIII‐ONO2 anion 5 instead of 2, as evidenced by NMR spectroscopy, EA and Sc‐XRD.
Explosion pressure and duration prediction using machine learning: A comparative study using classical models with Adam‐optimized neural network
Authors: Idris Ahmad Muzammil , Rusli Risza , Mohamed Moamen Elsayed , Ramli Ahmad Fakrul , Nasif Mohammad Shakir , Lim Jeng Shiun
Published: April 2024

The application of machine learning (ML) for the prediction of gas explosion pressure remains limited, and the prediction of the explosion duration is nearly non‐existent. A series of dispersion and subsequent explosion computational fluid dynamics (CFD) simulations were conducted to determine explosion pressure and duration values. These results were used to train classical ML models, that is, support vector regression (SVR), random forest (RF), and decision tree (DT) models. Additionally, a multi‐output Adam‐optimized artificial neural network (ANN) model was employed for performance comparison. All the models demonstrated respectable predictions for both parameters, while the RF model demonstrated the highest performance based on the metrics analyzed, followed by the DT model. The proposed gas volume and gas volume blockage ratio (gas‐VBR) emerged as the most crucial feature for predicting explosion pressure, while the monitoring point and gas‐VBR was the most important feature for explosion duration. It is recommended to consider the gas‐VBR feature in future studies rather than solely focusing on blockage ratio or obstacle location. The model proposed was compared with models from previous studies for predicting explosion pressure. The findings conclusively demonstrate that the multi‐output model outperforms the compared models, offering a notable advantage in its ability to predict both gas explosion pressure and duration.
“To prescribe or not to prescribe, that is the question”: Perspectives on opioid prescribing for chronic, cancer‐related pain from clinicians who treat pain in survivorship
Authors: Bulls Hailey W. , Hamm Megan , Wasilewski Julia , Olejniczak Donna , Bell Sarah G. , Liebschutz Jane M.
Published: April 2024

Background

Opioid pain management in cancer survivorship is a complex and understudied topic.

Methods

The authors conducted in‐depth, qualitative interviews to understand clinician approaches to opioid pain management in chronic cancer pain and to generate ideas for improvement. They used a rigorous, inductive, qualitative, descriptive approach to examine clinician (n = 20) perspectives about opioid pain management in survivorship, including oncologists (n = 5), palliative care clinicians (n = 8), primary care clinicians (n = 5), and pain management specialists (n = 2).

Results

The findings indicated that no consistent medical home exists for chronic pain management in cancer survivors and that there are fundamental differences in how each subspecialty approaches chronic pain management in survivorship (e.g., “Do we think of this as noncancer pain or cancer pain?… This is in this limbo zone—this gray zone—because it's cancer‐related pain, right?”). Simultaneously, clinicians are influenced by their peers' perceptions of their opioid prescribing decisions, sparking intraprofessional tension when disagreement occurs. In these instances, clinicians described overthinking and doubting their clinical decision‐making as well as a sense of judgment, pressure, and/or shame. Finally, clinicians acknowledged a fear of consequences for opioid prescribing decisions. Specifically, participants cited conflict with patients, sometimes escalating to aggression and threats of violence, as well as potential disciplinary actions and/or legal consequences.

Conclusions

Participants suggested that opportunities to improve chronic cancer pain care include developing clear, systematic guidance for chronic cancer pain management, facilitating clinician communication and consultation, creating tailored survivorship care plans in partnership with patients, and developing accessible, evidence‐based, complementary pain treatments.
Atomic Scale Insights into Reversible Oxygen Storage in Vanadium Oxide Thin Films
Authors: Missaoui Ghada , Wemhoff Piotr Igor , Nilius Niklas
Published: April 2024

Monolayer vanadium oxide films grown on Pt(111) can be reversibly switched between an oxygen‐poor and an oxygen‐rich composition, equivalent to V2O3 and V2O5, respectively. While the overall oxygen storage capacity of the film is quantified by X‐ray photoelectron spectroscopy, the atomic binding sites of the extra O species are determined by low‐temperature scanning tunneling microscopy and electron diffraction. In the O‐poor phase, the oxide takes the form of a honeycomb lattice that gets partially covered with vanadyl (V=O) groups at higher O exposure. Upon transition to the O‐rich phase, isolated V6O12 rings emerge in the film first, which then evolves towards a disordered O−V−O trilayer on the Pt(111) surface. Our works thus unravels the microscopic nature of reversible oxygen storage in a model system for heterogeneous catalysis.
Electrochemical Nitrogen Reduction to Ammonia at Ambient Condition on the (111) Facets of Transition Metal Carbonitrides
Authors: Iqbal Atef , Skulason Egill , Abghoui Younes
Published: April 2024

We conducted Density Functional Theory calculations to investigate a class of materials with the goal of enabling nitrogen activation and electrochemical ammonia production under ambient conditions. The source of protons at the anode could originate from either water splitting or H2, but our specific focus was on the cathode reaction, where nitrogen is reduced into ammonia. We examined the conventional associative mechanism, dissociative mechanism, and Mars‐van Krevelen mechanism on the (111) facets of the NaCl‐type structure found in early transition metal carbonitrides, including Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Sc, Y, and W. We explored the catalytic activity by calculating the free energy of all intermediates along the reaction pathway and constructing free energy diagrams to identify the steps that determine the reaction‘s feasibility. Additionally, we closely examined the potential for catalyst poisoning within the electrochemical environment, considering the bias required to drive the reaction. Furthermore, we assessed the likelihood of catalyst decomposition and the potential for catalyst regeneration among the most intriguing carbonitrides. Our findings revealed that the only carbonitride catalyst considered here exhibiting both activity and stability, capable of self‐regeneration and nitrogen‐to‐ammonia activation, is NbCN with a low potential‐determining step energy of 0.58 eV. This material can facilitate ammonia formation via a mixed associative‐MvK mechanism. In contrast, other carbonitrides of this crystallographic orientation are likely to undergo decomposition, reverting to their parent metals under operational conditions.
Cyclodextrins‐Based Polyrotaxanes: From Functional Polymers to Applications in Electronics and Energy Storage Materials
Authors: Du Ruichun , Bao Tianwei , Kong Deshuo , Zhang Qiuhong , Jia Xudong
Published: April 2024

The concept of polyrotaxane comes from the rotaxane structure in the supramolecular field. It is a mechanically interlocked supramolecular assembly composed of linear polymer chains and cyclic molecules. Over recent decades, the synthesis and application of polyrotaxanes have seen remarkable growth. Particularly, cyclodextrin‐based polyrotaxanes have been extensively reported due to the low‐price raw materials, good biocompatibility, and ease of modification. Hence, it is also one of the most promising mechanically interlocking supramolecules for wide industrialization in the future. Polyrotaxanes are widely introduced into materials such as elastomers, hydrogels, and engineering polymers to improve their mechanical properties or impart functionality to the materials. In these materials, polyrotaxane acts as a slidable cross‐linker to dissipate energy through sliding or assist in dispersing stress concentration in the cross‐linked network, thereby enhancing the toughness of the materials. Further, the unique sliding‐ring effect of cyclodextrin‐based polyrotaxanes has pioneered advancements in stretchable electronics and energy storage materials. This includes their innovative use in stretchable conductive composite and binders for anodes, addressing critical challenges in these fields. In this mini‐review, our focus is to highlight the current progress and potential wider applications in the future, underlining their transformative impact across various domains of material science.
The Isothermal and Non‐Isothermal Growth Behaviors of Ca2Nb2O7 in Molten Slag
Authors: Han Wensheng , Ran Mengjie , Chen Chang , Chen Wen
Published: April 2024

Calcium pyroniobate (Ca2Nb2O7) as a kind of lead‐free piezoelectric material has been applied for different fields, but the study of isothermal and non‐isothermal growth behaviors of Ca2Nb2O7 in the molten slag is infrequent. In this paper, the in situ thermal analyzer with a single hot thermocouple technique (SHTT) is used to study the growth behaviors of Ca2Nb2O7 in molten slag. In the isothermal temperatures, the Ca2Nb2O7 presents two kinds of growth morphology, including three dimensional (3D) rhombus growth and fibrous one dimensional (1D) growth. The 3D rhombus is grown under the range of 1608 to 1628 K. When the temperature further decreases to 1593 K, the growth behavior of Ca2Nb2O7 becomes fibrous in 1D. Growth velocity affected by the degree of supercooling may account for the phenomenon of two kinds of growth behaviors in different temperatures. In the non‐isothermal growth process, the cooling rate over 10 K min−1 contributes to multiple crystal nucleuses growth of Ca2Nb2O7. The cooling rate below 5 K min−1 leads to single nuclear growth. This paper provides a control guideline for Ca2Nb2O7 growth.
A Pyrophosphate Bifunctional Cathode with Inductive Effect for High–Voltage and Self–Charging Zinc Ion Battery
Authors: Deng Yifan , Li Hongcheng , Yan Yuekai , Zhang Minggang , Chang Peng , Mei Hui , Cheng Laifei , Zhang Litong
Published: April 2024

With the growing demand for new energy storage devices, rechargeable aqueous zinc ion batteries (ZIBs) have attracted widespread attention due to their low cost and high safety. Among the cathode materials for ZIBs, polyanionic–based cathode materials with high voltage, high stability, and low cost have great potential. In this paper, tetragonal Na2VOP2O7 was prepared using a simple sol–gel method. The discharge platform voltage amounted to 1.8 V and had good rate and cycle performance due to the inductive effect of pyrophosphate. Then, a protective layer of Zn–hydroxyapatite (ZnHAP) modification was applied to the cathode surface, which can inhibit the hydrolysis of vanadium ions. The capacity was enhanced by 19 % after modification and the capacity retention after 100 cycles was also higher. Interestingly, the Na2VOP2O7 cathode also possesses a self–charging effect, recovering to 48 % of its initial capacity with an open–circuit voltage (OCV) of 1.1 V within a certain period, and light exposure can reduce the self–charging time by 83 %. These beneficial results indicate that the pyrophosphate bifunctional cathode with inductive effect has a great potential to construct high–voltage and multifunctional zinc ion battery.
Social relationships, amyloid burden, and dementia: The ARIC‐PET study
Authors: Groechel Renée C. , Liu Albert C. , Liu Chelsea , Knopman David S. , Koton Silvia , Kucharska‐Newton Anna M. , Lutsey Pamela L. , Mosley Thomas H. , Palta Priya , Sharrett A. Richey , Walker Keenan A. , Wong Dean F. , Gottesman Rebecca F.
Published: April 2024

INTRODUCTION

This study aimed to assess whether social relationships in mid‐life reduce the risk of dementia related to amyloid burden.

METHODS

Participants in the Atherosclerosis Risk in Communities (ARIC) study were assessed for social support and isolation (visit 2; 1990–1992). A composite measure, “social relationships,” was generated. Brain amyloid was evaluated with florbetapir positron emission tomography (PET); (visit 5; 2012–2014). Incident dementia cases were identified following visit 5 through 2019 using ongoing surveillance. Relative contributions of mid‐life social relationships and elevated brain amyloid to incident dementia were evaluated with Cox regression models.

RESULTS

Among 310 participants without dementia, strong mid‐life social relationships were associated independently with lower dementia risk. Elevated late‐life brain amyloid was associated with greater dementia risk.

DISCUSSION

Although mid‐life social relationships did not moderate the relationship between amyloid burden and dementia, these findings affirm the importance of strong social relationships as a potentially protective factor against dementia.
New insights into the anticancer therapeutic potential of icaritin and its synthetic derivatives
Authors: Reyes‐Hernández Octavio Daniel , Figueroa‐González Gabriela , Quintas‐Granados Laura Itzel , Hernández‐Parra Hector , Peña‐Corona Sheila I. , Cortés Hernán , Kipchakbayeva Aliya , Mukazhanova Zhazira , Habtemariam Solomon , Leyva‐Gómez Gerardo , Büsselberg Dietrich , Sharifi‐Rad Javad
Published: April 2024

Icaritin is a natural prenylated flavonoid derived from the Chinese herb Epimedium. The compound has shown antitumor effects in various cancers, especially hepatocellular carcinoma (HCC). Icaritin exerts its anticancer activity by modulating multiple signaling pathways, such as IL‐6/JAK/STAT3, ER‐α36, and NF‐κB, affecting the tumor microenvironment and immune system. Several clinical trials have evaluated the safety and efficacy of icaritin in advanced HCC patients with poor prognoses, who are unsuitable for conventional therapies. The results have demonstrated that icaritin can improve survival, delay progression, and produce clinical benefits in these patients, with a favorable safety profile and minimal adverse events. Moreover, icaritin can enhance the antitumor immune response by regulating the function and phenotype of various immune cells, such as CD8+ T cells, MDSCs, neutrophils, and macrophages. These findings suggest that icaritin is a promising candidate for immunotherapy in HCC and other cancers. However, further studies are needed to elucidate the molecular mechanisms and optimal dosing regimens of icaritin and its potential synergistic effects with other agents. Therefore, this comprehensive review of the scientific literature aims to summarize advances in the knowledge of icaritin in preclinical and clinical studies as well as the pharmacokinetic, metabolism, toxicity, and mechanisms action to recognize the main challenge, gaps, and opportunities to develop a medication that cancer patients can use. Thus, our main objective was to clarify the current state of icaritin for use as an anticancer drug.
Analytical and behavioral characterization of 1‐dodecanoyl‐LSD (1DD‐LSD)
Authors: Kavanagh Pierce V. , Westphal Folker , Pulver Benedikt , Elliott Simon P. , Stratford Alexander , Halberstadt Adam L. , Brandt Simon D.
Published: April 2024

1‐Acetyl‐N,N‐diethyllysergamide (1A‐LSD, ALD‐52) was first synthesized in the 1950s and found to produce psychedelic effects similar to those of LSD. Evidence suggests that ALD‐52 serves as a prodrug in vivo and hydrolysis to LSD is likely responsible for its activity. Extension of the N1‐alkylcarbonyl chain gives rise to novel lysergamides, which spurred further investigations into their structure–activity relationships. At the same time, ALD‐52 and numerous homologues have emerged as recreational drugs (“research chemicals”) that are available from online vendors. In the present study, 1‐dodecanoyl‐LSD (1DD‐LSD), a novel N1‐acylated LSD derivative, was subjected to analytical characterization and was also tested in the mouse head‐twitch response (HTR) assay to assess whether it produces LSD‐like effects in vivo. When tested in C57BL/6J mice, 1DD‐LSD induced the HTR with a median effective dose (ED50) of 2.17 mg/kg, which was equivalent to 3.60 μmol/kg. Under similar experimental conditions, LSD has 27‐fold higher potency than 1DD‐LSD in the HTR assay. Previous work has shown that other homologues such as ALD‐52 and 1‐propanoyl‐LSD also have considerably higher potency than 1DD‐LSD in mice, which suggests that hydrolysis of the 1‐dodecanoyl moiety may be comparatively less efficient in vivo. Further investigations are warranted to determine whether the increased lipophilicity of 1DD‐LSD causes it to be sequestered in fat, thereby reducing its exposure to enzymatic hydrolysis in plasma and tissues. Further clinical studies are also required to assess its activity in humans and to test the prediction that it could potentially serve as a long‐acting prodrug for LSD.
Population distribution and drivers of habitat use for the Burrunan dolphins, Port Phillip Bay, Australia
Authors: Beddoe Jemima , Shimeta Jeff , Klaassen Marcel , Robb Kate
Published: April 2024

Bottlenose dolphin (Tursiops) populations, also described as the Burrunan dolphins, consist of a resident population of approximately 150 individuals in Port Phillip Bay (PPB), Victoria. Previous reports indicate distribution across a small southern region of PPB; however, little is known about their full distribution patterns across the entire PPB region. Here, we investigate the spatiotemporal distribution of the Burrunan dolphins across four zones representative of PPB benthic habitats and bathymetry to gain a better understanding of the potential drivers of the population's habitat use. Port Phillip Bay, Victoria, Australia. One hundred and twenty‐nine boat‐based surveys were undertaken between March 2015 and August 2021, encompassing 181 sightings. Generalised linear models (GLMs) were used to investigate annual, seasonal and zonal variation. We found no variation in sighting frequencies between years. Austral summer and winter had a significantly higher sighting frequency than autumn. We found that Burrunan dolphins utilise the entire bay, further extending the species range, and show a significantly higher number of sightings in the southern zone than in any other zones. Overlaying dolphin sightings with known oceanographic characteristics within PPB, we found bathymetry and benthic habitats were potential drivers for the Burrunan dolphins distribution and habitat use within the bay, with the dolphins significantly favouring the 5–10 and 10–15 m contour depths. These results show a more widespread distribution across the bay than previously documented. We recommend expansion of the current marine protected areas in the north and south of the bay. This study has increased our understanding of the vital habitat for the Burrunan dolphin populations. By providing evidence‐based conservation recommendations, we hope to improve and contribute to future research, conservation management plans and effective marine protected areas across PPB for the resident Burrunan dolphin population.
Managers of complex change? How United Nations treaty secretariats jointly govern institutional interplay in global environmental governance
Authors: Elsässer Joshua Philipp
Published: April 2024

Research on international bureaucracies, such as treaty secretariats, has predominantly focused on broadening our understanding of their role, function, and influence within their respective regulatory domains. However, the potential for treaty secretariats to manage situations of institutional overlap by coordinating with other agencies across policy areas has remained understudied. This article offers new empirical and theoretical insights for studying collective agency and coordination mechanisms in instances of institutional interaction within hybrid regime complexes. Specifically, it investigates how the treaty secretariats of the Rio Conventions under the United Nations employ joint interplay management as a means to improve institutional coherence within the climate change, biodiversity loss, and desertification nexus. Collectively, the public agencies aim to advance knowledge and discourse, influence norm‐building processes and regulation, or build capacity and support the joint implementation of policy objectives addressing the interlinked environmental problems. They do this by interacting with various actors across governance levels, including national governments, transnational initiatives, private actors, or civil society. By tracing the process linking joint activities with effects of such interactions, this qualitative case study makes a conceptual contribution by extrapolating a mechanistic theory for joint interplay management. The article demonstrates that treaty secretariats have to contend with challenges of resource allocation, diverging mandates, leadership priorities, and the degree of politicization and timing which frequently intervene stages of strategizing and executing joint activities. The results highlight that joint interplay management can be most impactful when secretariats employ orchestration practices through joint outreach and advocacy to advance coherent institutional responses to interdependent environmental problems.