bluuebunny/crossref_metadata_2025 huggingface dataset:
A Significant Two‐Dimensional Structural Transformation in a Coordination Polymer that Changes Its Electronic and Protonic Behavior
Authors: Jing Yao , Yoshida Yukihiro , Komatsu Tokutaro , Kitagawa Hiroshi
Published: May 2023

A 2D‐to‐2D (2D: two‐dimensional) structural transformation accompanying significant bond rearrangement and coordination environment change is demonstrated in a coordination polymer (CP) comprised of copper(II) ions and terephthalate (BDC2−) ligands for the first time. When immersed in water, a free‐standing membrane of 2D Cu(BDC)(DMF) (Cu‐1; DMF: N,N‐dimethylformamide) transforms into 2D Cu(BDC)(H2O)2 (Cu‐2) while maintaining its highly oriented layered structure. In the 2D sheet, paddlewheel‐type CuII dimers coordinated with four bidentate BDC ligands in a square‐planar array in Cu‐1 were released to form uniform aqua‐bridged CuII chains, which are cross‐linked with each other by unidentate BDC ligands, in Cu‐2. The present facile approach to implement the 2D‐to‐2D transformation accompanied by bond rearrangement, which is characteristic of CPs, leads to a marked increase in in‐plane magnetic susceptibility and proton conductivity. In situ experiments in support of theoretical calculations unveiled the energy diagram that governs the unique structural transformation.
The Formation of NaYF4 : Er3+, Yb3+ Nanocrystals Studied by In Situ X‐ray Scattering: Phase Transition and Size Focusing
Authors: Prins P. Tim , van der Bok Johanna C. , van Swieten Thomas P. , Hinterding Stijn O. M. , Smith Andy J. , Petukhov Andrei V. , Meijerink Andries , Rabouw Freddy T.
Published: May 2023

β‐NaYF4 nanocrystals are a popular class of optical materials. They can be doped with optically active lanthanide ions and shaped into core‐multi‐shell geometries with controlled dopant distributions. Here, we follow the synthesis of β‐NaYF4 nanocrystals from α‐NaYF4 precursor particles using in situ small‐angle and wide‐angle X‐ray scattering and ex situ electron microscopy. We observe an evolution from a unimodal particle size distribution to bimodal, and eventually back to unimodal. The final size distribution is narrower in absolute numbers than the initial distribution. These peculiar growth dynamics happen in large part before the α‐to‐β phase transformation. We propose that the splitting of the size distribution is caused by variations in the reactivity of α‐NaYF4 precursor particles, potentially due to inter‐particle differences in stoichiometry. Rate equation modeling confirms that a continuous distribution of reactivities can result in the observed particle growth dynamics.
A comprehensive proposed model for gas separation prediction of mixed matrix membranes containing tubular fillers
Authors: Feijani Elahe Ahmadi , Rezakazemi Mashallah
Published: May 2023

In this study, a comprehensive model based on composite modulus prediction model named Takayanagi is rendered which can reasonably describe gas performance of tubular filler contained mixed matrix membrane (MMMs) by considering any possible interfacial morphology. Interphase thickness (t), interphase permeability (Pi), and percolation threshold concept are included in proposed model to accurate description of the MMM performance. Since tubular fillers can be in different surface area with the same chemistry, mechanical properties are useful for determination of interphase thickness based on Pukanszky approach. On the other hand, the maximum separation potential of tubular filler can be estimated by the proposed model. In order to examine the proposed model, polyvinylidene fluoride based MMMs containing pristine and acid modified multiwalled carbon nanotube are fabricated and characterized. The interphase morphology and contribution of carbon nanotubes in gas permeability of the constructed MMMs are interpreted in details by the proposed model.
Learn how to distinguish between service animals, emotional support animals, and assistance animals
Authors: Gutierrez Iván Resendiz
Published: May 2023

In the past few years, an increasing number of college students have expressed interest in bringing their service animals, emotional support animals (ESAs), or assistance animals to campus to help them manage a variety of physical and mental health issues. Although most institutions have policies and procedures regarding animals on campus, colleges and universities should be prepared to handle complex or unique requests. Recently, some of the more unexpected ESA requests from individuals with disabilities have involved some particularly exotic animals — including a beehive, a baby kangaroo, and a large peacock.
Determine when to apply supportive measures, accommodations, or remedies in Title IX process
Authors: McCarthy Claudine
Published: May 2023

CLEARWATER, FLORIDA — If a student complainant involved in a Title IX process at your institution requests extra support, accommodations, adjustments, or remedies, it can be confusing to determine which is which and if or how you're required to comply.
Did court dismiss Title IX claim against university?
Authors: Lyerly Eric
Published: May 2023

Tel Aviv University is a public university located in Israel. A TAU student, who was also a U.S. Citizen, was called to appear before the university's professionalism committee after he was accused of “sexually inappropriate behavior” and unprofessionalism.
Structures and Mechanisms of a Novel Bacterial Transport System for Fatty Acids
Authors: Zhai Liting , Chou Jonathan Chiu‐Chun , Oo Hannah , Dassama Laura M. K.
Published: May 2023

Bacterial acquisition of metabolites is largely facilitated by transporters with unique substrate scopes. The tripartite ATP‐independent periplasmic (TRAP) transporters comprise a large family of bacterial proteins that facilitate the uptake of a variety of small molecules. It has been reported that some TRAP systems encode a fourth protein, the T component. The T‐component, or TatT, is predicted to be a periplasmic‐facing lipoprotein that enables the uptake of metabolites from the outer membrane. However, no substrates were revealed for any TatT and their functional role(s) remained enigmatic. We recently identified a homolog in Methylococcus capsulatus that binds to sterols, and herein, we report two additional homologs that demonstrate a preference for long‐chain fatty acids. Our bioinformatics, quantitative analyses of protein‐ligand interactions, and high‐resolution crystal structures suggest that TatTs might facilitate the trafficking of hydrophobic or lipophilic substrates and represent a new class of bacterial lipid and fatty acid transporters.
CYPArm2 is a CYP450 Monooxygenase with Protoilludene 13‐Hydroxylase Activity Involved in the Biosynthesis of Armillyl Orsellinate‐Type Sesquiterpenoids
Authors: McElroy Christopher , Engels Benedikt , Meusinger Reinhard , Jennewein Stefan
Published: May 2023

The melleolides are a family of structurally and functionally diverse sesquiterpenoids with potential applications as fungicides, antimicrobials, and cancer therapeutics. The initial and terminal steps of the biosynthesis pathway in Armillaria spp. have been characterized, but the intermediate steps are unclear. Biosynthetic gene clusters in A. mellea and A. gallica were shown to encode a terpene cyclase, a polyketide synthase, and four CYP450 monooxygenases. We have characterized CYPArm3, which is responsible for the hydroxylation of Δ‐6‐protoilludene, but the functions of the other CYP450s remain to be determined. Here we describe CYPArm2, which accepts Δ‐6‐protoilludene and 8α‐hydroxy‐6‐protoilludene as substrates. To investigate the products in more detail, we generated recombinant Saccharomyces cerevisiae strains overexpressing CYPArm2 in combination with the previously characterized protoilludene synthase and 8α‐hydroxylase. Using this total biosynthesis approach, sufficient quantities of product were obtained for NMR spectroscopy. This allowed the identification of 8α,13‐dihydroxy‐protoilludene, confirming that CYPArm2 is a protoilludene 13‐hydroxylase.
Aortocoronary dissection during percutaneous coronary interventions for chronic total occlusion: Insights from the PROGRESS‐CTO registry
Authors: Kostantinis Spyridon , Rempakos Athanasios , Simsek Bahadir , Karacsonyi Judit , Allana Salman S. , Alaswad Khaldoon , Basir Mir Babar , Krestyaninov Oleg , Khelimskii Dmitrii , Gorgulu Sevket , Davies Rhian E. , Benton Stewart M. , Khatri Jaikirshan J. , Poommipanit Paul , Choi James W. , Jaber Wissam A. , Rinfret Stephane , Nicholson William , Aygul Nazif , Altunkeser Bulent Behlul , ElGuindy Ahmed M. , Abi Rafeh Nidal , Goktekin Omer , Mastrodemos Olga C. , Rangan Bavana V. , Sandoval Yader , Burke M. Nicholas , Brilakis Emmanouil S.
Published: May 2023

Background

Aortocoronary dissection is a potentially serious complication of chronic total occlusion (CTO) percutaneous coronary intervention (PCI).

Methods

We examined the incidence, mechanisms, treatment, and outcomes of aortocoronary dissection among 12,117 CTO PCIs performed between 2012 and 2022 in a large multicenter CTO PCI registry.

Results

The incidence of aortocoronary dissection was 0.2% (n = 27). Most aortocoronary dissections occurred in the right coronary artery (96.3%, n = 26). The baseline clinical characteristics of patients with and without aortocoronary dissection were similar, except for dyslipidemia, which was less common in patients with aortocoronary dissection (70.4% vs. 86.0%; p = 0.019). The retrograde approach was used more commonly among cases complicated by aortocoronary dissection (59.3% vs. 31.0%; p = 0.002). Technical (74.1% vs. 86.6%; p = 0.049) and procedural (70.4% vs. 85.2%; p = 0.031) success rates were lower among aortocoronary dissection cases, with a similar incidence of in‐hospital major adverse cardiovascular events (3.7% vs. 2.0%; p = 0.541). Of the 27 patients with aortocoronary dissection, 19 (70.4%) were treated with ostial stenting and 8 (29.6%) were treated conservatively without subsequent adverse clinical outcomes. No patients required emergency surgery. Follow‐up was available for 22 patients (81.5%): during a mean follow up of 767 (±562) days, the incidence of in‐stent restenosis was 11.1% (n = 3).

Conclusions

Aortocoronary dissection occurred in 0.2% of CTO PCIs performed by experienced operators, was associated with lower technical and procedural success, and was treated most commonly with ostial stenting. None of the patients required emergency cardiac surgery.
Quantitative flow ratio modulated by intracoronary optical coherence tomography for predicting physiological efficacy of percutaneous coronary intervention
Authors: Ding Daixin , Tu Shengxian , Li Yingguang , Li Chunming , Yu Wei , Liu Xun , Leone Antonio Maria , Aurigemma Cristina , Romagnoli Enrico , Vergallo Rocco , Trani Carlo , Wijns William , Burzotta Francesco
Published: May 2023

Background

The combination of coronary imaging assessment and blood flow perturbation estimation has the potential to improve percutaneous coronary intervention (PCI) guidance.

Objectives

We aimed to evaluate a novel method for fast computation of Murray law‐based quantitative flow ratio (μQFR) from coregistered optical coherence tomography (OCT) and angiography (OCT‐modulated μQFR, OCT‐μQFR) in predicting physiological efficacy of PCI.

Methods

Patients treated by OCT‐guided PCI in the OCT‐arm of the Fractional Flow Reserve versus Optical Coherence Tomography to Guide RevasculariZAtion of Intermediate Coronary Stenoses trial (FORZA, NCT01824030) were included. Based on angiography and OCT before PCI, simulated residual OCT‐μQFR was computed by assuming full stent expansion to the intended‐to‐treat segment. Plaque composition was automatically characterized using a validated artificial intelligence algorithm. Actual post‐PCI OCT‐μQFR pullback was computed based on coregistration of angiography and OCT acquired immediately after PCI. Suboptimal functional stenting result was defined as OCT‐μQFR ≤ 0.90.

Results

Paired simulated residual OCT‐μQFR and actual post‐PCI OCT‐μQFR were obtained in 76 vessels from 74 patients. Simulated residual OCT‐μQFR showed good correlation (r = 0.80, p < 0.001), agreement (mean difference = −0.02 ± 0.02, p < 0.001), and diagnostic concordance (79%, 95% confidence interval: 70%–88%) with actual post‐PCI OCT‐μQFR. Actual post‐PCI in‐stent OCT‐μQFR had a median value of 0.02 and was associated with left anterior descending artery lesion location (β = 0.38, p < 0.001), higher baseline total plaque burden (β = 0.25, p = 0.031), and fibrous plaque volume (β = 0.24, p = 0.026).

Conclusions

This study based on patients enrolled in a prospective OCT‐guidance PCI trial shows that simulated residual OCT‐μQFR had good correlation, agreement, and diagnostic concordance with actual post‐PCI OCT‐μQFR. In OCT‐guided procedures, OCT‐μQFR in‐stent pressure drop was low and was significantly predicted by pre‐PCI vessel/plaque characteristics.
Behavior of Constitutional Dynamic Networks: Competition, Selection, Self‐sorting in Cryptate Systems
Authors: Osypenko Artem , Cabot Rafel , Armao Joseph J. , Kovaříček Petr , Santoro Antonio , Lehn Jean‐Marie
Published: May 2023

Understanding dynamic systems is a crucial step toward the design of complex matter. Here, we aim to study the behavior of Constitutional Dynamic Networks (CDNs) in conditions of dynamic competition, taking cryptands and metal cations as a test bed. The CDNs of cryptates were analyzed by NMR spectroscopy. The experimental results were complemented by extensive numerical simulations, based on a large amount of thermodynamic and kinetic data available in the literature for cryptates. Although the CDN′s output is a result of the interplay between the individual stability constants of the complexes in a mixture, the overall effect may be governed by only one – the most thermodynamically stable member of a network. Significantly, these findings indicate that an increase in complexity (multiplicity and connectivity) of a system may, in conditions of dynamic competition, result in “simplexity”, i. e. a simplification of the output of the system.
Pillar[5]arene‐Based AIE Supramolecular Polymer Networks Exhibiting Various Fluorescence to Achieve Visible Surveillance
Authors: Sheng Lan , Liu Hui , Hu Ziqing , Ji Xiaofan
Published: May 2023

Supramolecular polymer networks (SPNs) based on pillar[n]arene are widely studied and it is known that evolution from linear polymers to SPNs occurs as a progressive process, which is of importance to monitor the detailed morphology throughout the process. Yet, the current reports related to that distinction by employing fluorescence approach have realized confined success, it still remains a challenge to distinguish the various states visually. Herein, a fluorescent group of the pyrene benzohydrazonate‐based (PBHZ‐based) derivative is introduced into the pillar[5]arene based SPNs gained from host–guest recognition, enabling the visual monitoring during the formation of SPNs. The whole visual detection was based on the fluorescence color transition ranging from blue to green relying on the gradual aggregated PBHZ molecules upon the increasing cross‐linking degree. Besides, the stimuli‐responsiveness of this SPNs was confirmed that increasing the temperature or adding a reducing agent would reduce the cross‐linking degree.
Isoform‐Selective Fluorescent Labeling of 14‐3‐3σ by Acrylamide‐Containing Fusicoccins
Authors: Tanaka Kenta , Hatano Yoshiya , Ohkanda Junko
Published: May 2023

The 14‐3‐3 family of proteins is central to the regulation of signaling pathways driven by serine/threonine kinases. In humans, 14‐3‐3 consists of seven highly conserved isoforms, yet the function of each isoform remains to be fully elucidated. Synthetic agents capable of isoform‐specific fluorescent labeling of 14‐3‐3 would provide a useful tool for studying in depth the biological roles of isoforms. In this study, the 14‐3‐3σ isoform was evaluated, which possesses a unique Cys38, and a natural product‐based fluorescent labeling agent was designed by introducing an acrylamide group and a fluorescent dye to fusicoccin (FC). In vitro evaluation demonstrated that 12‐hydroxy 1 and 2 exhibit 14‐3‐3σ selective labeling activity over 14‐3‐3ζ in the presence of a mode‐3 phospholigand. Furthermore, 2 was shown to label 14‐3‐3σ in cell lysate in the presence of a C‐terminal mode‐3 phosphopeptide derived from ERα, with no apparent nonspecific labeling. These results indicate that 2 is capable of selective fluorescent detection of 14‐3‐3σ upon binding to mode‐3 phospholigand under biologically relevant conditions.
Efficient resource allocation algorithms for multihop D2D approach in 5G network
Authors: Chauhan Srishti , Gupta Amol , T Velmurugan , S Nandakumar
Published: May 2023

Now the 5G network systems are expected to enhance their throughput. Device‐to‐device (D2D) communication is one such technique that offers an effective solution. The existing cellular user (CU) communication must be ensured that this solution had minimized its interference with it. Hence, designing methods for resource allocation for D2D transmission is also important. Such allocation will maximize network throughput without causing much interference with the present communication. Apart from these, it ensures delay minimization and achieves fairness among user data rates. But when distance is increased, an extension from direct D2D communication (single‐hop) to multi‐hop is necessary. At the same time, its objectives shall be retained. In the proposed work, initially, a comparative study is done on different algorithms for multi‐hop (two‐hop) D2D communication pairs. While studying different algorithms such as random allocation (RA), graph allocation (GA), particle swamp optimization (PSO), and technique for order preference by similarity to the ideal solution (TOPSIS), they are also analyzed, looking for the possibility of a particular combination of them to achieve specific objectives. The realized method has improved performance even in the situation of an increase in distance. The arrived two methods also support a better data rate. The first method allocates resources based on orthogonal sharing. The second method is for allocating resources to them that have cellular orientation. The simulated results exhibit the improved capability of the proposed methods. The method based on the graph to allocate the mentioned resources functions better. Finally, for throughput and data rates, PSO and TOPSIS techniques are implemented.
Solar Driven 15.7% Hydrogen Conversion by Harmony of Light Harvesting, Electron Transporting Bridge, and S‐Defection in a Self‐Assembled Microscale CuS/rGO/CP Photoanode
Authors: Kim Sujeong , Seo Boseok , Park Hyerim , Im Younghwan , Do Jeong Yeon , Kwak Byung Sub , Son Namgyu , Kim Minkyu , Kang Misook
Published: May 2023

CuS is an encouraging photoelectrode candidate that meets the essential requirements for efficient solar‐to‐hydrogen production, but it has not been thoroughly studied. A CuS light absorber layer is grown by the self‐assembly of copper and sulfur precursors on a carbon paper (CP) electrode. Simultaneously, rGO is introduced as a buffer layer to control the optical and electrical properties of the absorber. The well‐ordered microstructural arrangement suppresses the recombination loss of electrons and holes owing to enhanced charge‐carrier generation, separation, and transport. The potential reaching 10 mA cm−2 in 1.0 m KOH solution is significantly lowered to 0.87 V, and the photocurrent density at 1.23 V is 94.7 mA cm−2. The computational result reveals that the potential‐determining step is sensitive to O* stability; the lower stability of O* in the thin layer of CuS/rGO decreases the free‐energy gap between the initial and final states of the potential‐determining step, resulting in a lowering of the onset potential. The faradaic efficiency for the photoelectrochemical oxygen evolution reaction in the optimized 2CuS/1rGO/CP photoanode is 98.60%, and the applied bias photon‐to‐current and the solar‐to‐hydrogen efficiencies are 11.2% and 15.7%, respectively, and its ultra‐high performance is maintained for 250 h. These record‐breaking achievement indices may be a trigger for establishing a green hydrogen economy.
Structure Regulation of Electric Double Layer via Hydrogen Bonding Effect to Realize High‐Stability Lithium‐Metal Batteries
Authors: Liu Sheng , Shu Chaozhu , Yan Yu , Du Dayue , Ren Longfei , Zeng Ting , Wen Xiaojuan , Xu Haoyang , Wang Xinxiang , Tian Guilei , Zeng Ying
Published: May 2023

The interfacial chemistry of solid electrolyte interphases (SEI) on lithium (Li) electrode is directly determined by the structural chemistry of the electric double layer (EDL) at the interface. Herein, a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed (p‐hydroxybenzoic acid (pHA) is selected as proof‐of‐concept). According to the molecular dynamics (MD) simulation and density functional theory (DFT) calculation results, the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL, reduces the lowest unoccupied molecular orbital (LUMO) energy level of anions in the EDL, and the number of free solvent molecules, which promotes the formation of inorganic species‐enriched SEI and eventually achieves the dendrite‐free Li deposition. Based on this strategy, Li||Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm−2, and the long‐term cycle stability of Li||Li cells is increased to 1200 h. In addition, the full cell pairing with the commercial LiFePO4 (LFP) cathodes exhibits stable cycling performance at 1C, with a capacity retention close to 90% after 200 cycles.
Early diagnostic value of high‐sensitivity cardiac troponin T for cancer treatment‐related cardiac dysfunction: a meta‐analysis
Authors: Lv Xinfang , Pan ChenLiang , Guo Huan , Chang Juan , Gao Xiang , Wu Xue , Zhi Xiaodong , Ren Chunzhen , Chen Qilin , Jiang Hugang , Zhao Xinke , Liu Kai , Li Yingdong
Published: May 2023

Early diagnosis of cancer treatment‐related cardiac dysfunction (CTRCD) is important as cancer therapy increases the risk of cardiac dysfunction. High‐sensitivity cardiac troponin T (hs‐cTnT) is a highly specific marker of myocardial injury. However, its diagnostic value for CTRCD has not been systematically evaluated. This meta‐analysis aimed to evaluate whether hs‐cTnT could be used as an early diagnostic biomarker for CTRCD. We systematically surveyed PubMed, Embase, Cochrane Library, and Web of Science databases for studies of hs‐cTnT for the diagnosis of CTRCD before 1 April 2022. Patients of all ages and all cancer types who underwent echocardiographic left ventricular ejection fraction assessment and blood hs‐cTnT and received anticancer therapy (including chemotherapy, radiotherapy, targeted therapy, immune checkpoint inhibitors, and other treatments) were included in this study, resulting in a total of eight studies with 1294 patients. The occurrence of CTRCD was associated with elevated hs‐cTnT [sensitivity: 0.78, 95% confidence interval (CI): 0.64–0.88; specificity: 0.75, 95% CI: 0.59–0.86; area under the curve (AUC): 0.83, 95% CI: 0.80–0.86]. We further performed subgroup analysis and found that the AUC of hs‐cTnT elevation for the diagnosis of CTRCD increased from 0.83 to 0.90 (95% CI: 0.87–0.92) at 3–6 months, suggesting a higher early diagnostic value of hs‐cTnT compared with echocardiography for CTRCD. In terms of clinical applicability, the Fagan plot showed pre‐test and post‐test probabilities of 51% and 9%, respectively, indicating that hs‐cTnT testing can improve the accuracy of clinical diagnosis of CTRCD. However, it was not possible to determine the optimal cut‐off value for early diagnosis of CTRCD with hs‐cTnT. The Deeks funnel plot was largely symmetrical (P = 0.74); hence, publication bias was not observed. Hs‐cTnT allowed early CTRCD diagnosis at 3–6 months. However, further high‐quality research is needed to determine the optimal cut‐off value for early CTRCD diagnosis with this biomarker.
Adsorption Behavior of U(VI) and Re(VII) on Iron Sulfide Nanoparticles Modified with Titanate Nanotubes: Mechanism and Performance Insights
Authors: Pan Yixin , Zhang Pengkun , Huang Rui , Kou Jisheng
Published: May 2023

A novel nanocomposite (TNTs‐FeS) was developed by anchoring ferrous sulfide (FeS) nanoparticles immobilized on titanate nanotubes (TNTs) by hydrothermal method to remove U(VI) and Re(VII) from aqueous solution, and the removal mechanism and efficiency were examined. The experimental results showed that the TNTs can effectively improve the dispersibility and stability of FeS. The environmental conditions, including initial solution pH, initial concentration, equilibrium time, and dosage, played an important role in the remediation process, which can affect the immobilization efficiency significantly. The maximum quantity removal of U(VI) and Re(VII) was 291.67 and 226.23 mg/g at pH of 6.0 and 12.0. The adsorption kinetics and the equilibrium isotherms of U(VI) and Re(VII) all fitted well with the pseudo‐second‐order model (R2>0.99) and the Freundlich model (R2>0.99). The main mechanism of removal by TNTs‐FeS was electrostatic attraction, chemical reduction, and surface complexation. Thus, TNTs‐FeS composites exhibited a high potential to remove U(VI) and Re(VII) heavy metal ions from the surface and groundwater.
Optimization of Mn‐Mg‐Al Mixed Oxides Composition on their Activity towards the Total Oxidation of Aromatic and Oxygenated VOCs
Authors: El Khawaja Rebecca , Rochard Guillaume , Genty Eric , Poupin Christophe , Siffert Stéphane , Cousin Renaud
Published: May 2023

A series of mixed oxides (Mn‐Mg‐Al) is prepared by coprecipitation via a hydrotalcite route with different manganese ratios. Structural, textural, and redox properties are studied by XRD, N2‐sorption, H2‐TPR, and XPS techniques. MnxMg6‐xAl2‐O mixed oxides (with 0≤x≤6) are tested in the total oxidation of ethanol and toluene, two probe molecules representing respectively oxygenated and aromatic VOCs. Catalysts with higher manganese contents have shown the best catalytic performance for the oxidation of both ethanol and toluene. The surface activity of the materials is mainly related to the presence of manganese species in three different oxidation states (+II, +III, and +IV) in the bulk and on the material's surface. Since high Mn‐content catalysts showed similar physicochemical properties and catalytic activity, Mn4Mg2‐O is selected as the optimal composition of these materials. Furthermore, its aging test is compared to that of noble metal‐based commercial catalysts (Pd/γ‐Al2O3).
Differential electrochemical behaviour of phytofabricated and chemically synthesized silver nanoparticles towards hydrogen peroxide sensing**
Authors: Mahato Kuldeep , Baranwal Anupriya , Kumari Rohini , Srivastava Ananya , Pratap Azad Uday , Chandra Pranjal
Published: May 2023

Silver nanoparticles (AgNPs) are one of the most widely used nanomaterials for biomedical applications. However, the impact of its synthesis by chemical and plant‐mediated routes on its differential electrochemical behaviour has not been examined till date. Here, we report for the first time the differential study of the electrochemical behaviour of the AgNPs synthesized by different routes. First, the AgNPs were obtained by different routes (chemical and phytofabrication) and extensively characterized to compare their physical properties. Thereafter, a comparison of electron transfer kinetics between chemically synthesized (Ag−C) and phyto‐fabricated (Ag‐Phy) nanoparticles (NPs) has been studied by electrochemical techniques such as potentiodynamic cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). To further investigate the electrocatalytic properties of both types of AgNPs, we have used the peroxide moieties (H2O2), and the Ag−C NPs‐based sensor probe has been reported to have four times better sensitivity than the Ag−Phy NPs‐based sensor. The AgNPs modified sensor probes have also been tested in real‐world environments to explore the consistency of their performance in complex matrices by using clinical urine samples, where we found comparable sensitivity to the standard conditions.
Diffusion kinetics of CuCo2O4 nanorods for next‐generation solid state sodium‐ion hybrid supercapacitor
Authors: Jhankal Deependra , Khan Mohammad Saquib , Yadav Bhanu , Shakya Preeti , Bhardwaj Nikita , Jhankal K. K. , Sachdev K.
Published: May 2023

In the current study, we report a straightforward and affordable sol‐gel preparation approach for the fabrication of spinel CuCo2O4 nanorods for sodium ion‐based hybrid supercapacitor. The morphological and structural analysis shows that appropriate purity nanorods of CuCo2O4 are formed with good stoichiometry. The electrochemical study of CuCo2O4 nanorods reveals that the electrode has highest specific capacitance of 367 F g−1 at 1 A g−1 in 1 M Na2SO4 electrolyte. Evaluation of the diffusion kinetics of sodium ions through detailed electrochemical evaluations of cyclic voltammogram (CV) showing the charge storage kinetics of CuCo2O4 is primarily performed through the diffusive limited mechanisms, suggesting the battery‐like behavior of CuCo2O4 electrode. Hybrid supercapacitor (HSC) device is fabricated by utilizing CuCo2O4 for positive and reduced graphene oxide (rGO) for negative electrodes material. The polymer gel electrolyte is used in the form of hydrogel membrane made of PVA and Na2SO4, and the HSC device (rGO || CuCo2O4) exhibits energy density of 9.18 Wh kg−1. Therefore, sodium‐ion hybrid supercapacitor electrode materials for this investigation are established using a comprehensive electrochemical kinetics.
Dose and time–response effect of photobiomodulation therapy on glycemic control in type 2 diabetic patients combined or not with hypoglycemic medicine: A randomized, crossover, double‐blind, sham‐controlled trial
Authors: Scontri Clara Maria Cobra Branco , de Castro Magalhães Flávio , Damiani Ana Paula Moraes , Hamblin Michael R. , Zamunér Antonio Roberto , Ferraresi Cleber
Published: May 2023

Photobiomodulation therapy (PBMt) combined or not with oral hypoglycemic medication has not been investigated in type 2 diabetes (T2DM) patients. All 10 T2DM patients were assessed randomly at 6 different occasions (3 with and 3 without regular oral hypoglycemic medication). Capillary glycemia was assessed after overnight fast (pre‐prandial), 1 h postprandially (standardized meal, 338 kcal), and 30 min, 3 h, 6 h, 12 h post‐PBMt (830 nm; 25 arrays of LEDs, 80 mW/array). Three doses (0 J—sham, 100 J, 240 J per site) were applied bilaterally on quadriceps femoris muscles, hamstrings, triceps surae, ventral upper arm and forearm; and randomly combined or not with oral hypoglicemic medication, totaling six different therapies applied for all 10 TDM2 patients (PBMt sham, PBMt 100 J, PBMt 240 J, PBMt sham + medication, PBMt 100 J + medication, PBMt 240 J + medication). Cardiac autonomic control was assessed by heart rate variability (HRV) indices. Without medication, there was reduction in glycemia after all PBMt doses, with 100 J as the best dose that persisted until 12 h and presented lower area under the curve (AUC). With medication, glycemia decreased similarly among doses. No differences between 100 J and sham + medication, but AUC was significantly lower after 100 J, suggesting better glycemic control. Low frequency component of HRV increased after sham + medication and 100 J, suggesting higher sympathetic activation. PBMt showed time– and dose–response effect to reduce glycemia in T2DM patients. Effects on HRV were consistent with glycemic control.
Trapped in housing insecurity: Socioecological barriers to housing access experienced by intimate partner violence survivors from marginalized communities
Authors: Kulkarni Shanti J. , Notario Heidi
Published: May 2023

Homelessness and intimate partner violence (IPV) do not impact all communities equally. Survivors from marginalized communities—that is communities that have been historically and structurally excluded from social, economic, and political resources—face additional challenges weathering IPV and housing crises. Understanding the housing experiences of marginalized survivors is necessary to achieve housing equity for all survivors. Community‐based participatory research methods were utilized to convene 14 listening sessions (7 primary/7 validation) with Black and Latinx IPV survivors with intersectional identities (n = 92). Listening sessions were held in community‐based locations including a church, health clinic, social service agency, and private residence. The last five validation sessions were conducted virtually on Zoom due to COVID pandemic protocols. All listening sessions were digitally recorded and transcribed verbatim. Latinx population listening sessions were conducted in Spanish and were implemented and translated with attention to linguistic justice principles. The research team used a modified constructivist grounded theory approach for data analysis. Four overarching themes (and seven subthemes) related to survivors' housing experiences emerged: (1) safety and healing challenges, including living in unhealthy physical environments, not being safe in their homes, and contending with community violence, sexual exploitation threats, and eviction fears; (2) formal service fragmentation/bureaucracy that hampered access to housing resource information and resources; (3) resource scarcity associated with limited affordable housing stock; and (4) systemic oppression resulting from discriminatory treatment and gentrification. Comprehensive multileveled approaches are needed to disrupt the cycle of housing insecurity for IPV survivors from marginalized communities.
Compressed 4‐day workweek for dental faculty retention and recruitment
Authors: Afshari Fatemeh S. , Guajardo Leticia , Kramer Jill M. , Musawi Ammar , Regasamy Venugopalan Shankar , Sykes‐Smith Anita
Published: May 2023

Faculty recruitment and retention are major concerns faced by dental schools across the country. This increase in faculty shortage impacts training the next generation of clinicians and oral health care delivery in dental institutions, which together will exacerbate challenges related to access to dental care. The objective of this paper is to propose a compressed workweek as an incentive to improve recruitment, retention, and faculty well‐being. There are several well‐documented benefits of the 4‐day workweek which include employee wellness, increased job satisfaction, happiness, and improved perception of personal worth. Cost savings may be also realized with this schedule, as expenses related to transportation and dependent care costs could potentially decrease. Altogether, these benefits have been shown to lead to reduced absenteeism, anxiety, stress, and burnout. This perspective piece will discuss how the 4‐day workweek could be implemented in dental institutions, along with the benefits and challenges. Given the shortage of clinical faculty throughout the United States, we recommend this approach not only as a means to attract recent graduates to academia but also to ensure the retention of those who provide clinical instruction.
Impact of the Interdecadal Pacific Oscillation on tropical Indian Ocean sea surface height: An assessment from CMIP6 models
Authors: Chinta Veeranjaneyulu , Du Yan , Hong Yu , Chen Zesheng , Chowdary Jasti S.
Published: May 2023

This study examined the sea level (SL) changes on the interdecadal timescale in the tropical Indian Ocean (TIO) in response to the Interdecadal Pacific Oscillation (IPO) in 20 Coupled Model Intercomparison Project Phase 6 (CMIP6) models. The analysis suggests that the interdecadal sea level pattern variation in the Thermocline Ridge of the Indian Ocean (TRIO) area coincides with the IPO phases and is mainly caused by fluctuations of surface forcing over the TIO. Changes in tropical wind stress curl (WSC) mainly induce the SL variability on the interdecadal timescale associated with IPO in the TRIO region in both observations and models. The stochastic wind forcing and its interaction with the ocean's internal variability produce significant interdecadal SL fluctuation in the southeast Indian Ocean. We evaluated the ability of 20 CMIP6 models to capture interdecadal variations in sea level teleconnections. We found that about 75% of models reproduce decadal fluctuations related to IPO pretty well. The interdecadal variations of the SL in the western TIO emerge primarily in response to westward propagating downwelling Rossby waves induced by the WSC in the central‐south TIO in MMM, and models as in observations. Pacific IPO‐related anomalies primarily spread through the oceanic pathways of the Maritime Continent in the eastern Indian Ocean. Further, the IPO induces changes in the western Indian Ocean WSC through atmospheric pathways, which in turn causes Rossby waves to move westward, affecting the southwest Indian SL. Almost all the models and MMM show interdecadal SL variations in TIO associated with IPO. This study is beneficial as interdecadal prediction research on SL has a significant societal need.
Kinetics of the cross‐reaction of CH3O2 + HO2 radicals measured in the Highly Instrumented Reactor for Atmospheric Chemistry
Authors: Østerstrøm Freja F. , Onel Lavinia , Brennan Alexander , Parr Joseph M. , Whalley Lisa K. , Seakins Paul W. , Heard Dwayne E.
Published: May 2023

The sensitive Fluorescence Assay by Gas Expansion (FAGE) method has been used to detect methyl peroxy (CH3O2) and hydroperoxyl (HO2) radicals after their conversion by titration with excess NO to methoxy (CH3O) and hydroxyl (OH) radicals, respectively, to study the kinetics of the reaction of CH3O2 + HO2 radicals. The rate coefficient of the reaction was measured in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) at 1000 mbar of synthetic air at T = 268–344 K, selectively detecting both radicals. Using a numerical model to fit both CH3O2 and HO2 radical temporal decays globally at each temperature investigated, rate coefficients for the reaction have been obtained. The room temperature rate coefficient was found to be kCH3O2 +HO2(295 K) = (4.6 ± 0.7) × 10−12 molecule−1 cm3 s−1 (2σ errors) and the temperature dependence of the rate coefficient can be characterized in Arrhenius form by kCH3O2 + HO2(268 K < T < 344 K) = (5.1 ± 2.1) × 10−13 × exp((637 ± 121)/T) cm3 molecule−1 s−1. The rate coefficients obtained here are 14%–16% lower than the literature recommended values with an uncertainty which is reduced significantly compared to previous reports.
Temperature regulates Synechococcus population dynamics seasonally and across the continental shelf
Authors: Stevens Bethany L. F. , Crockford E. Taylor , Peacock Emily E. , Neubert Michael G. , Sosik Heidi M.
Published: May 2023

Hourly, year‐round flow cytometry has made it possible to relate seasonal environmental variability to the population dynamics of the smallest, most abundant phytoplankton on the Northeast US Shelf. To evaluate whether the insights from these data extend to Synechococcus farther from shore, we analyze flow cytometry measurements made continuously from the underway systems on 21 cruises traveling between the Martha's Vineyard Coastal Observatory (MVCO) and the continental shelf break. We describe how seasonal patterns in Synechococcus, which have been documented in detail at MVCO, occur across the region with subtle variation. We find that the underlying relationship between temperature and division rate is consistent across the shelf and can explain much of the observed spatial variability in concentration. Connecting individual cell properties to annual and regional patterns in environmental conditions, these results demonstrate the value of autonomous monitoring and create an improved picture of picophytoplankton dynamics within an economically important ecosystem.
A Versatile Method to Create Perfusable, Capillary‐Scale Channels in Cell‐Laden Hydrogels Using Melt Electrowriting
Authors: Liu Emily I. , Footner Elizabeth , Quigley Anita , Baker Chris , Foley Peter , Pirogova Elena , Kapsa Robert M. I. , O'Connell Cathal D.
Published: May 2023

A major obstacle toward creating human‐scale artificial tissue models is supplying encapsulated cells with oxygen and other nutrients throughout the construct. In particular, creating channels in hydrogels that match the resolution and density of the smallest blood capillaries (≤10 µm) remains highly challenging. Here, a novel method is demonstrated where polycaprolactone fibers printed using melt‐electrowriting are encapsulated in cell‐laden hydrogels and then physically removed to produce hollow, perfusable channels. This technique produces a range of channel diameters (10–41 µm) with circular cross‐sections and in hydrogels representing various crosslinking mechanisms. The channels can be formed as interconnected grids, hierarchically branched patterns, or stacked in layers with ≈200 µm channel spacing, thus matching average capillary density in the human body. Alternatively, selective removal of fibers from a melt electrowriting grid can generate perfusable channels within a reinforcing fiber network. This method can be performed in the presence of cells, with human fibroblasts exhibiting encapsulated in gelatin methacryloyl showing no detectable cytotoxic effects. This technique is a promising approach for creating perfusable channels with very small diameters within cell‐laden hydrogel matrices, with potential applications including in vitro tissue models and hydrogel microfluidics.
Beyond Yield Optimization: The Impact of Organosolv Process Parameters on Lignin Structure
Authors: Bergrath Jonas , Rumpf Jessica , Burger René , Do Xuan Tung , Wirtz Michaela , Schulze Margit
Published: May 2023

When optimizing the process parameters of the acidic ethanolic organosolv process, the aim is usually to maximize the delignification and/or lignin purity. However, process parameters such as temperature, time, ethanol and catalyst concentration, respectively, can also be used to vary the structural properties of the obtained organosolv lignin, including the molecular weight and the ratio of aliphatic versus phenolic hydroxyl groups, among others. This review particularly focuses on these influencing factors and establishes a trend analysis between the variation of the process parameters and the effect on lignin structure. Especially when larger data sets are available, as for process temperature and time, correlations between the distribution of depolymerization and condensation reactions are found, which allow direct conclusions on the proportion of lignin's structural features, independent of the diversity of the biomass used. The newfound insights gained from this review can be used to tailor organosolv lignins isolated for a specific application.
Longitudinal Synaptic Loss in Primary Tauopathies: An In Vivo [11C]UCB‐J Positron Emission Tomography Study
Authors: Holland Negin , Jones P. Simon , Savulich George , Naessens Michelle , Malpetti Maura , Whiteside David J. , Street Duncan , Swann Peter , Hong Young T. , Fryer Tim D. , Rittman Timothy , Mulroy Eoin , Aigbirhio Franklin I. , Bhatia Kailash P. , O'Brien John T. , Rowe James B.
Published: May 2023

Background

Synaptic loss is characteristic of many neurodegenerative diseases; it occurs early and is strongly related to functional deficits.

Objective

In this longitudinal observational study, we determine the rate at which synaptic density is reduced in the primary tauopathies of progressive supranuclear palsy (PSP) and corticobasal degeneration (CBD), and we test the relationship with disease progression.

Methods

Our cross‐sectional cohort included 32 participants with probable PSP and 16 with probable CBD (all amyloid‐negative corticobasal syndrome), recruited from tertiary care centers in the United Kingdom, and 33 sex‐ and age‐matched healthy control subjects. Synaptic density was estimated by positron emission tomography imaging with the radioligand [11C]UCB‐J that binds synaptic vesicle 2A. Clinical severity and cognition were assessed by the PSP Rating Scale and the Addenbrooke's cognitive examination. Regional [11C]UCB‐J nondisplaceable binding potential was estimated in Hammersmith Atlas regions of interest. Twenty‐two participants with PSP/CBD had a follow‐up [11C]UCB‐J positron emission tomography scan after 1 year. We calculated the annualized change in [11C]UCB‐J nondisplaceable binding potential and correlated this with the change in clinical severity.

Results

We found significant annual synaptic loss within the frontal lobe (−3.5%, P = 0.03) and the right caudate (−3.9%, P = 0.046). The degree of longitudinal synaptic loss within the frontal lobe correlated with the rate of change in the PSP Rating Scale (R = 0.47, P = 0.03) and cognition (Addenbrooke's Cognitive Examination–Revised, R = −0.62, P = 0.003).

Conclusions

We provide in vivo evidence for rapid progressive synaptic loss, correlating with clinical progression in primary tauopathies. Synaptic loss may be an important therapeutic target and outcome variable for early‐phase clinical trials of disease‐modifying treatments. © 2023 The Authors. Movement Disorders published by Wiley Periodicals LLC on behalf of International Parkinson and Movement Disorder Society.
Orthoplastic limb reconstruction using free fibula flap after trauma: Outcomes from a retrospective European multicenter study
Authors: Di Summa Pietro G. , de Schoulepnikoff Camille , Guillier David , Cigna Emanuele , Jiga Lucian P. , Jandali Zaher , Vezza Daniele , Giacalone Francesco , Ciclamini Davide , Battiston Bruno , Elia Rossella , Maruccia Michele
Published: May 2023

Background

Free vascularized fibula flap represents the gold standard vascularized bone graft for the management of segmental long bone defects after traumatic injury. The current study represents the largest retrospective multicenter data collection on the use of free fibula flap (FFF) for extremities' orthoplastic reconstruction after trauma aiming to highlight current surgical practice and to set the basis for updating current surgical indications.

Methods

The study is designed as a retrospective analysis of prospectively collected data between 2009 and 2021 from six European University hospitals. Patients who underwent fibula flap reconstruction after acute traumatic injury (AF) or as a late reconstruction (LF) after post‐traumatic non‐union of upper or lower limb were included. Only extra‐articular, diaphyseal fracture were included in the study. Surgical data were collected. Time to bone healing and complications were reported as clinical outcomes.

Results

Sixty‐two patients were included in the study (27 in the AF group and 35 in the LF group). The average patients' age at the time of the traumatic event was 45.3 ± 2.9 years in the AF group and 41.1 ± 2.1 years in the LF group. Mean bone defect size was 7.7 ± 0.6 cm for upper limb and 11.2 ± 1.1 cm (p = .32) for lower limb. Bone healing was uneventful in 69% of treated patients, reaching 92% after complementary procedures. Bone healing time was 7.6 ± 1.2 months in the acute group and 9.6 ± 1.5 months in the late group. An overall complication rate of 30.6% was observed, with a higher percentage of late bone complications in the LF group (34%), mostly non‐union cases.

Conclusions

FFF reconstruction represents a reliable and definitive solution for long bone defects with bone healing reached in 92% cases with a 8.4 months of average bone healing time.