bluuebunny/crossref_metadata_2025_split huggingface dataset:
Towards Understanding the Molecular Mechanisms of Immunogenic Cell Death
Authors: Xiong Xiaolin , Wang Yuan , Zou Taotao 
Published: November 2022

AbstractThe discovery of immunogenic cell death (ICD) by small molecules (e. g., chemotherapeutic drugs) intrigued medicinal chemists and led them to exploit anticancer agents with such a trait because ICD agents provoke anticancer immune responses in addition to their cytotoxicity. However, the unclear molecular mechanism of ICD hampers further achievements in drug development. Fortunately, increasing efforts have been made in this area in recent years by using either chemical or biological approaches. Here, we review the current achievements towards understanding the mechanisms of small molecule‐induced ICD effects. Based on the established role of the unfolded protein response (UPR) in ICD, we classify the mechanisms of different inducers by their dependency on UPR. Key proteins and pathways with important implications are discussed in depth. We also give our perspectives on the research strategies for future investigation in this field.
The Buoy Effect: Surface Enrichment of a Pt Complex in IL Solution by Ligand Design
Authors: Hemmeter Daniel , Kremitzl Daniel , Schulz Peter S. , Wasserscheid Peter , Maier Florian , Steinrück Hans‐Peter 
Published: November 2022

AbstractThe targeted enrichment of a Pt complex with an ionic liquid (IL)‐derived ligand system in IL solution is demonstrated by using angle‐resolved X‐ray photoelectron spectroscopy. When the ligand system is complemented with fluorinated side chains, the complex accumulates strongly at the IL/gas interface, while in an equivalent solution of a complex without these substituents no such effect could be observed. This buoy‐like behavior induces strong population of the complex at the outermost molecular layer close to surface saturation, which was studied over a range from 5 to 30 %mol. The surface enrichment was found to be most efficient at the lowest concentration, which is particularly favorable for catalytic applications such as supported ionic‐liquid‐phase (SILP) catalysis.
X‐Ray Triggered Coordination‐Bond Breakage in Dysprosium‐Organic Framework and its Impact on Magnetic Properties
Authors: Zou Qian , Wang Guo‐Lu , Chen Yi‐Qing , Huang Xin‐Da , Wen Ge Hua , Qin Ming‐Feng , Bao Song‐Song , Zhang Yi‐Quan , Zheng Li‐Min 
Published: November 2022

AbstractPhotosensitive lanthanide‐based single‐molecule magnets (Ln−SMM) are very attractive for their potential applications in information storage, switching, and sensors. However, the light‐driven structural transformation in Ln−SMMs hardly changes the coordination number of the lanthanide ion. Herein, for the first time it is reported that X‐ray (λ=0.71073 Å) irradiation can break the coordination bond of Dy−OH2 in the three‐dimensional (3D) metal‐organic framework Dy2(amp2H2)3(H2O)6 ⋅ 4H2O (MDAF‐5), in which the {Dy2(OPO)2} dimers are cross‐linked by dianthracene‐phosphonate ligands. The structural transformation proceeds in a single‐crystal‐to‐single‐crystal (SC‐SC) fashion, forming the new phase Dy2(amp2H2)3(H2O)4 ⋅ 4H2O (MDAF‐5‐X). The phase transition is accompanied by a significant change in magnetic properties due to the alteration in coordination geometry of the DyIII ion from a distorted pentagonal bipyramid in MDAF‐5 to a distorted octahedron in MDAF‐5‐X.
Synthesis of a Bifunctionalized Glycosylphosphatidylinositol (GPI) Anchor Useful for the Study of GPI Biology
Authors: Mullapudi Venkanna Babu , Craig Kendall C. , Guo Zhongwu 
Published: November 2022

AbstractA new, bifunctional glycosylphosphatidylinositol (GPI) derivative containing the highly conserved core structure of all natural GPI anchors with a photoactivable diazirine in the lipid chain and clickable alkynes in the glycan was synthesized by a convergent [3+2] glycosylation strategy with late stage protecting group manipulation and regioselective phosphorylation. The challenges of this synthesis were due to the presence of several distinctive functional groups in the synthetic target, which complicated the protection tactics, in addition to the inherent difficulties associated with GPI synthesis. This bifunctional GPI derivative can cross‐react with molecules in proximity upon photoactivation and be subsequently labeled with other molecular tags via click reaction. Therefore, it should be a valuable probe for biological studies of GPIs, such as analysis of GPI‐interacting membrane proteins, and gaining insights into their functional mechanisms.
Long‐Acting Insulin‐Zwitterionic Polymer Conjugate Mitigates Hypoglycemia
Authors: Zeng Zhipeng , Hou Wangmeng , Hu Zhitao , Liu Lixin , Liu Zhijia , Shi Yi , Li Mingqiang , Chen Yongming 
Published: November 2022

AbstractInsulin, a main medication to control glycemia of type 1 and advanced type 2 diabetes, faces problems of a short half‐life and poor stability during its clinical use. Zwitterionic polymer shows unique properties of antifouling and low immunogenicity. Here, we have synthesized a new insulin‐zwitterionic polymer conjugate (INS‐PMPC) through grafting‐from strategy by controlled radical polymerization. Apart from showing excellent stability upon mechanical agitation, the resulting INS‐PMPC conjugate provided over 20 h of glycemic control due to improved pharmacokinetics in diabetic mice with one single subcutaneous injection. Most importantly, this insulin‐zwitterionic polymer conjugate significantly decreases the incidence of hypoglycemia.
Syntheses of η1‐Alkyl‐η3‐Allyl‐η5‐Cyclopentadienyl Cobalt(III) Complexes and Their Use in Low‐temperature Atomic Layer Deposition of Cobalt‐Containing Thin Films
Authors: Lu Ke , Zhu Jiahao , Wang Jialiang , Wa Qingbo , Guo Zheng , Xiong Wei , Gao Yuan , Lei Renbo , Cheng Bichu , Wang Xinwei 
Published: November 2022

AbstractHerein, we report the design and scalable synthesis of three new Co(III) complexes, which have an unusual hydrocarbon η1‐alkyl‐η3‐allyl‐η5‐cyclopentadienyl ligation structure, from the reactions of readily available cobalt(II) compound CoCl2(PPh3)2 and biomass material β‐pinene via C−C bond activation. These Co(III) complexes are air‐stable, fairly volatile, and thermally stable, so they are excellent candidates as the metal precursors for the vapor deposition of cobalt‐containing thin films. As a demonstration, we show that the Co(III) complex of [(3’‐5’‐η,1‐σ)‐methylene(2,2,4‐trimethyl‐4‐cyclohexene‐1,3‐diyl)](η5‐methylcyclopentadienyl)Co (i. e. (seco‐pinene)(MeCp)Co) is well suited for the atomic layer deposition (ALD) of Co3O4 and CoS2 thin films, and the deposited Co3O4 and CoS2 films are able to conformally cover trench structures with a fairly high aspect ratio of 10 : 1.
Inverse material parameter estimation of patient‐specific finite element models at the carotid bifurcation: The impact of excluding the zero‐pressure configuration and residual stress
Authors: Johnston Robert D. , Ghasemi Milad , Lally Caitríona 
Published: November 2022

AbstractThe carotid bifurcation experiences a complex loading environment due to its anatomical structure. Previous in‐vivo material parameter estimation methods often use simplified model geometries, isotropic hyperelastic constitutive equations or neglect key aspects of the vessel, such as the zero‐pressure configuration or residual stress, all of which have independently been shown to alter the stress environment of the vessel wall. Characterizing the location of high stress in the vessel wall has often been proposed as a potential indicator of structural weakness. However, excluding the afore‐mentioned zero‐pressure configuration, residual stress and patient‐specific material parameters can lead to an incorrect estimation of the true stress values observed, meaning that stress alone as a risk indicator of rupture is insufficient. In this study, we investigate how the estimated material parameters and overall stress distributions in geometries of carotid bifurcations, extracted from in‐vivo MR images, alter with the inclusion of the zero‐pressure configuration and residual stress. This approach consists of the following steps: (1) geometry segmentation and hexahedral meshing from in‐vivo magnetic resonance images (MRI) at two known phases; (2) computation of the zero‐pressure configuration and the associated residual stresses; (3) minimization of an objective function built on the difference between the stress states of an “almost true” stress field at two known phases and a “deformed” stress field by altering the input material parameters to determine patient‐specific material properties; and (4) comparison of the stress distributions throughout these carotid bifurcations for all cases with estimated material parameters. This numerical approach provides insights into the need for estimation of both the zero‐pressure configuration and residual stress for accurate material property estimation and stress analysis for the carotid bifurcation, establishing the reliability of stress as a rupture risk metric.
Subcutaneous implantable cardioverter‐defibrillator: a systematic review of comparative effectiveness and safety
Authors: Wolf Sarah , Götz Gregor , Wernly Bernhard , Wild Claudia 
Published: November 2022

AbstractThis systematic review evaluated the clinical effectiveness and safety of subcutaneous implantable cardioverter‐defibrillator (S‐ICD) in patients at an increased risk of sudden cardiac death and with an ICD indication for primary or secondary prevention. A systematic literature search was conducted in four databases (Medline via Ovid, Embase, the Cochrane Library, and HTA‐INAHTA). Randomized controlled trials (RCTs) and controlled observational studies with ≥100 S‐ICD patients and a low to moderate risk of bias were eligible for inclusion. The studies' quality and the available evidence's strength were assessed using the Cochrane risk of bias tool, the ROBINS‐I tool, and the Grading of Recommendations, Assessment, Development, and Evaluation (GRADE) approach. One RCT, a post hoc analysis of the RCT (n = 849) and four controlled observational studies (n = 7149) were included. The quality of the available evidence was graded as low to very low, except for the primary composite endpoint of the RCT, which was rated as moderate quality. After 4 years, the RCT showed that S‐ICD was non‐inferior to TV‐ICD regarding the composite endpoint of inappropriate shocks and device‐related complications (68 [15.1%] vs. 68 [15.7%], hazard ratio [HR] 0.99, 95% confidence interval [CI] [0.71, 1.39], non‐inferiority margin 1.45, P = 0.001). The RCT and two observational studies reported statistically significantly fewer lead complications in S‐ICD patients (after 4 years: 1.4% vs. 6.6%, HR 0.24, 95% CI [0.10, 0.54]; after 3 years: 0.3% vs. 2.3%, P = 0.03; and after 5 years: 0.8% vs. 11.5%, P = 0.03). Identified evidence about appropriate and inappropriate shocks was inconclusive: The RCT detected statistically significantly more appropriate shocks in patients with S‐ICD (83 [19.2%] vs. 57 [11.5%], HR 1.52, 95% CI [1.08, 2.12], P = 0.02), whereas one observational study showed a statistically significantly lower rate in the S‐ICD group (9.9%, 95% CI [7.0, 13.9], vs. 13.9%, 95% CI [10.8, 17.8], P = 0.003). Regarding inappropriate shocks, one observational study reported statistically significantly higher rates in the S‐ICD cohort (11.9% vs. 7.5%, P = 0.007), whereas the RCT and two other observational studies did not detect a statistically significant difference between the treatment groups (P > 0.05). None of the included studies showed a statistically significant difference in overall mortality and shock efficacy between patients with S‐ICD and TV‐ICD (P > 0.05). The available evidence is insufficient to show the superiority of S‐ICD compared with TV‐ICD, hindering the widespread use of the technology. Results of the recently completed ATLAS trial are to be awaited, and the anticipated role of the S‐ICD needs to be clearly formulated.
Origins of the Reactivity in 1,3‐Dipolar Cycloadditions of Acyl Isocyanide Ylides
Authors: Alfonso‐Ramos Javier E. , Van Lommel Ruben , Hernández‐Castillo David , De Proft Frank , González‐Alemán Roy , Van der Eycken Erik V. , Ojeda‐Carralero Gerardo M. 
Published: November 2022

Abstract1,3‐Dipolar cycloadditions are the preferred method to generate five‐membered heterocyclic rings. Surprisingly, cycloadditions based on acyl‐isocyanide ylides have remained underexplored by the chemical community. Acyl‐isocyanide ylides readily react with dipolarophiles, such as substituted alkenes, to yield Δ1‐pyrroline derivatives. As an explanation for the observed reactivity of this reaction is lacking, extensive density functional theory calculations were performed to scrutinize the mechanistic features of the transformation. Herein we explain the experimental outcome of the reaction using a variety of reactivity theories and predict opposed regioselectivity for electron‐poor and electron‐rich dipolarophiles. With the insights obtained, we hope to incentivize the design of new cycloaddition reactions based on the acyl‐isocyanide ylides motif.
CuMoO4 Catalyzed Csp2−Se Cross‐Coupling of Aryl Bromide and Iodide with Diaryldiselenides in Water
Authors: Choudhury Prabhupada , Kumar Pradhan Amit , Jena Soumyaranjan , Kumar Sahoo Bikash , Kumar Sahu Santosh , Kumar Behera Pradyota , Behera Papita , Swain Amlan , Rout Laxmidhar 
Published: November 2022

AbstractIn this work, an oxo‐bridged bimetallic CuMoO4 catalyst for Csp2−Se cross‐coupling of diaryldiselenides with aryl‐halides is reported. The current discovery is noteworthy, as the catalyst is eco‐friendly, easily accessible, air‐stable, and recyclable. The methodology exhibits broad substrate scope and the catalytic system tolerates common functional groups. The protocol uses aryl iodide and bromides as electrophile instead of boronic acids. This is the first example of using an oxo‐ bridged copper based bimetallic catalyst for Csp2−Se cross‐coupling reactions in water. C−Cl bond remains intact during reaction.
Electrochemical sensing platform based on the use of ZnONPs and MWCNTs as CPE modifiers for a selective and sensitive determination of polyamine spermine in the urine sample
Authors: Stojanović Zorica S. , Đurović Ana D. , Kravić Snežana Ž. , Ashrafi Amir M. , Richtera Lukáš 
Published: November 2022

AbstractA simple electroanalytical procedure has been developed for the determination of polyamine spermine using the ZnONPs‐MWCNTs‐CPE sensor. Spermine has been irreversibly oxidized on a modified electrode at a potential of +0.92 V versus Ag/AgCl (KCl, 3.5 mol L−1). The developed sensor demonstrated a respective linear response in borate buffer pH 8.5 from 2 μmol L−1 to 100 μmol L−1, with a detection limit of 0.300 μmol L−1 and quantification limit of 0.998 μmol L−1. The proposed sensor showed high reproducibility (RSD = 2.58 %), stability, robustness, and no obvious interference effects of several inorganic ions and organic molecules. The obtained results demonstrated excellent performance during the determination of the spermine in human urine samples with satisfactory recovery results (98.41–101.34 %), offering promising opportunities for practical clinical analysis.
How does over two decades of active wood reintroduction result in changes to stream channel features and aquatic habitats of a forested river system?
Authors: Pess George R. , McHenry Michael L. , Liermann Martin C. , Hanson Karrie M. , Beechie Timothy J. 
Published: November 2022

AbstractSince the late 1980s and early 1990s, wood reintroduction has been a commonly assessed stream restoration technique. Many of the efforts have focused on short‐term, localized physical changes and response of salmonids to wood reintroduction. Few have examined how long‐term, spatially extensive increases in wood loadings alter stream channel morphology and the geomorphic processes responsible for these changes. We used before and after photos as well as a wood storage survey with tagged restoration logs in a small, low‐elevation Western Washington watershed to characterize the effects of 23 years of wood additions. In the ~6 km of wood placement we saw an increase in wood loading and channel‐spanning logjams, which contributed to deeper and more frequent pools, a reduction in particle size, increases in sediment storage, reduced stream width, vegetation re‐establishment in the riparian zone, and increased development and maintenance of floodplain channels. The largest geomorphic changes occurred due to restoration wood effectively storing pieces moving downstream. These findings imply that the cumulative habitat restoration actions and associated changes to stream habitat conditions are identifiable through comparison of historical and current photos as well as more quantitative habitat metrics. It also demonstrates that wood placement that simulates the function of large key, stable pieces accelerates habitat recovery within basins subjected to historic logging.
Divergence and introgression among the virilis group of Drosophila
Authors: Yusuf Leeban H. , Tyukmaeva Venera , Hoikkala Anneli , Ritchie Michael G. 
Published: November 2022

Abstract
Speciation with gene flow is now widely regarded as common. However, the frequency of introgression between recently diverged species and the evolutionary consequences of gene flow are still poorly understood. The virilis group of Drosophila contains 12 species that are geographically widespread and show varying levels of prezygotic and postzygotic isolation. Here, we use de novo genome assemblies and whole-genome sequencing data to resolve phylogenetic relationships and describe patterns of introgression and divergence across the group. We suggest that the virilis group consists of three, rather than the traditional two, subgroups. Some genes undergoing rapid sequence divergence across the group were involved in chemical communication and desiccation tolerance, and may be related to the evolution of sexual isolation and adaptation. We found evidence of pervasive phylogenetic discordance caused by ancient introgression events between distant lineages within the group, and more recent gene flow between closely related species. When assessing patterns of genome-wide divergence in species pairs across the group, we found no consistent genomic evidence of a disproportionate role for the X chromosome as has been found in other systems. Our results show how ancient and recent introgressions confuse phylogenetic reconstruction, but may play an important role during early radiation of a group.
Hope and sadness: Balancing emotions in tobacco control mass media campaigns aimed at smokers
Authors: O'Hara Blythe J. , Owen Katherine B. , Bauman Adrian E. , Dunlop Sally , Phongsavan Philayrath , Furestad Erin , Scott Nicola , Freeman Becky 
Published: November 2022

AbstractIssue addressedAustralia has smoking prevalence of less than 15% among adults, but there are concerns that the rates of decline have stabilised. Sustained mass media campaigns are central to decreasing prevalence, and the emotions evoked by campaigns contribute to their impact. This study investigates the association between potential exposure to campaigns that evoke different emotions on quitting salience (thinking about quitting), quitting intentions and quitting attempts.MethodsData on quitting outcomes were obtained from weekly cross‐sectional telephone surveys with adult smokers and recent quitters between 2013 and 2018. Campaign activity data were collated, and population‐level potential campaign exposure was measured by time and dose.ResultsUsing multivariate analyses, a positive association between potential exposure to ‘hope’ campaigns and thinking about quitting and intending to quit was noted, but no association was seen with quit attempts. Potential exposure to ‘sadness’ evoking campaigns was positively associated with quitting salience and negatively associated with quit attempts, whereas those potentially exposed to campaigns evoking multiple negative emotions (fear, guilt and sadness) were approximately 30% more likely to make a quit attempt.ConclusionsThis study suggests a relationship between the emotional content of campaigns, quitting behaviours. Campaign planners should consider campaigns that evoke negative emotions for population‐wide efforts to bring about quitting activity alongside hopeful campaigns that promote quitting salience and quitting intentions. The emotional content of campaigns provides an additional consideration for campaigns targeting smokers and influencing quitting activity.So what?This study demonstrates the importance of balancing the emotional content of campaigns to ensure that campaign advertising is given the greatest chance to achieve its objectives. Utilising campaigns that evoke negative emotions appear to be needed to encourage quitting attempts but maintaining hopeful campaigns to promote thinking about quitting and intending to quit is also an important component of the mix of tobacco control campaigns.
Challenges and innovations in access to community‐based rural primary care services during the Covid‐19 pandemic in Australia
Authors: O’Sullivan Belinda 
Published: November 2022

AbstractBackgroundAccess to primary care is a significant issue for rural populations. The Covid‐19 pandemic imposed a unique operating environment for rural General Practice enabling accessible services. This study aimed to explore the challenges and innovations rural General Practices experienced in promoting accessible primary care during a year of the pandemic.MethodsLongitudinal semi‐structured interviews were done with key informants (General Practitioners or Practice Managers) from purposefully selected General Practices from different rural towns in different subregions. Interviews occurred at three stages of the pandemic, June 2020–June 2021. They explored participant perspectives of the emerging challenges and innovatinos as they sought to support accessible primary care services during the pandemic. The data were thematically coded using a deductive framework of access challenges and innovations over time.ResultsOf 12 practices approached, 11 key informants responded, providing around 30 h of interview data. The challenges and innovations related to access, changed over time as the pandemic evolved. A common theme concerned reflexive action. Practices had been on a journey during the pandemic to embed new planning processes, digital health options and to innovate to protect and support patients and staff to sustain access.ConclusionThis study provides useful insights into the challenges and innovations experienced in rural general practice during the Covid‐19 pandemic to reflect on models, strategies and approaches that can apply to promote access to rural primary care services going forward.