bluuebunny/crossref_metadata_2025 huggingface dataset:
Aldehyde‐Based Inhibitors of the Peptidoglycan O‐Acetylesterase Ape
Authors: Voskoboinyk Dmytro , Mahmoodi Niusha , Lin Chang Sheng‐Huei , Murphy Michael E. P. , Tanner Martin E.
Published: April 2023

The O‐acetylation of the muramic acid residues in peptidoglycan (PG) is a modification that protects the bacteria from lysis due to the action of lysozyme. In Gram‐negative bacteria, deacetylation is required to allow lytic transglycosylases to promote PG cleavage during cell growth and division. This deacetylation is catalyzed by O‐acetylpeptidoglycan esterase (Ape) which is a serine esterase and employs covalent catalysis via a serine‐linked acyl enzyme intermediate. Loss of Ape activity affects the size and shape of bacteria and dramatically reduces virulence. In this work, we report the first rationally designed aldehyde‐based inhibitors of Ape from Campylobacter jejuni. The most potent of these acts as a competitive inhibitor with a Ki value of 13 μM. We suspect that the inhibitors are forming adducts with the active site serine that closely mimic the tetrahedral intermediate of the normal catalytic cycle. Support for this notion is found in the observation that reduction of the aldehyde to an alcohol effectively abolishes the inhibition.
c‐Jun‐mediated JMJD6 restoration enhances resistance of liver cancer to radiotherapy through the IL‐4‐activated ERK pathway
Authors: Liu Yong , Sui Aixia , Sun Jirui , Wu Yifan , Liu Fuquan , Yang Yang
Published: April 2023

Radiotherapy is widely used in the treatment of liver cancer, but the efficacy can be limited by radioresistance. In this study, we attempt to delineate the possible molecular mechanism of c‐Jun‐regulated Jumonji domain‐containing protein 6/interleukin 4/extracellular signal‐regulated kinase (JMJD6/IL‐4/ERK) axis in radioresistance of liver cancer. The expression of c‐Jun was quantified in liver cancer tissues and cell lines, and the results indicated that c‐Jun was upregulated in liver cancer tissues and cells. We further illustrated the role of c‐Jun following gain‐ and loss‐of‐function strategies in malignant phenotypes of liver cancer cells. It was established that c‐Jun elevated JMJD6 expression and augmented the malignancy and aggressiveness of liver cancer cells. The in vivo effects of c‐Jun on radioresistance in liver cancer were validated in nude mice, in response to IL‐4 knockdown or the ERK pathway inhibitor, PD98059. In the presence of JMJD6 upregulation, the expression of IL‐4 was elevated in mice with liver cancer, which enhanced the radiation resistance. Moreover, knockdown of IL‐4 inactivated the ERK pathway, thereby reversing the radiation resistance caused by overexpressed JMJD6 in tumor‐bearing mice. Taken together, c‐Jun augments the radiation resistance in liver cancer by activating the ERK pathway through JMJD6‐upregulated IL‐4 transcription.
Computed tomography‐derived membranous septum length as predictor of conduction abnormalities and permanent pacemaker implantation after TAVI: A meta‐analysis of observational studies
Authors: Sá Michel Pompeu , Van den Eynde Jef , Jacquemyn Xander , Erten Ozgun , Rodriguez Roberto , Goldman Scott , Coady Paul M. , Gnall Eric , Gray William A. , Jarrett Harish , Abramson Sandra V. , Clavel Marie‐Annick , Pibarot Philippe , Ramlawi Basel
Published: April 2023

Background

Permanent pacemaker implantation (PPI) after transcatheter aortic valve implantation (TAVI) is associated with higher risk of mortality and rehospitalization for heart failure. Efforts to prevent conduction abnormalities (CA) requiring PPI after TAVI should be made. The membranous septum (MS) length and its interaction with implantation depth (ID–ΔMSID) could provide useful information about the risk of CA/PPI following TAVI.

Objectives

To identify MS length and ΔMSID as predictors of CA/PPI following TAVI.

Methods

Study‐level meta‐analysis of studies published by September 30, 2022.

Results

Eighteen studies met our eligibility including 5740 patients. Shorter MS length was associated with a significantly higher risk of CA/PPI (per 1 mm decrease: odds ratio [OR] 1.60, 95% confidence interval [CI] 1.28–1.99, p < 0.001). Similarly, lower ΔMSID was associated with a significantly higher risk of CA/PPI (per 1 mm decrease: OR 1.75, 95% CI 1.32–2.31, p < 0.001). Meta‐regression analyses revealed a statistically significant modulation of the effect of shorter MS length and lower ΔMSID on the outcome (CA/PPI) by balloon postdilatation (positive regression coefficients with p < 0.001); with increasing use of balloon postdilatation, the effect of shorter MS length and lower ΔMSID on the outcome increased. MS length and ΔMSID demonstrated excellent discriminative abilities, with diagnostic ORs equaling 9.49 (95% CI 4.73–19.06), and 7.19 (95% CI 3.31–15.60), respectively.

Conclusion

Considering that short MS length and low ΔMSID are associated with higher risk of CA and PPI, we should include measurement of MS length in the pre‐TAVI planning with MDCT and try to establish optimal ID values before the procedure to avoid CA/PPI.
Optical Super‐Localisation of Single Nanoparticle Nucleation and Growth in Nanodroplets
Authors: Ciocci Paolo , Valavanis Dimitrios , Meloni Gabriel N. , Lemineur Jean‐François , Unwin Patrick R. , Kanoufi Frédéric
Published: April 2023

Invited for this issue's Front Cover are the groups of Prof. Frédéric Kanoufi, Université Paris Cité‐CNRS (France), and Prof. Patrick Unwin, University of Warwick (United Kingdom), collaborating under the EU Horizon 2020 ‘Single‐entity Nanoelectrochemistry’ programme. The cover picture illustrates the use of their hybrid technique to investigate the dynamics of the electrodeposition of individual Ag nanoparticles within an ensemble. The particles are represented by band members whose individual performances can be monitored. Read the full text of the Research Article at 10.1002/celc.202201162.
A context‐specific conceptual framework of evidence synthesis to improve childhood cancer health outcomes and resource use in Egypt: Using real‐world data and addressing the implementation gaps
Authors: Soliman Ranin
Published: April 2023

Introduction

Given the large numbers of children with cancer in Egypt, the limited resources, and inferior survival outcomes, there is a need to better target resources to improve outcomes efficiently based on evidence. Nevertheless, there is a gap in knowledge about childhood cancer health outcomes and resource use in Egypt. This commentary presents a “context‐specific” conceptual framework of evidence synthesis to improve childhood cancer health outcomes and resource use in a resource‐limited setting in Egypt, using real‐world data and addressing the implementation gaps.

Methods

Real‐world data is defined as data relating to health status and/or the delivery of health services routinely collected from various sources outside the contexts of randomized controlled trials that can be used to conduct prospective/retrospective observational research studies.

Results

To better address this context‐specific clinical problem, the conceptual framework of evidence synthesis proposes to generate three types of evidence using hybrid research methods; (1) Real‐world evidence (obtained from observational studies based on routinely collected data from local context); (2) systematic evidence from the literature (systematic review); and (3) qualitative evidence based on experts' opinions in the local setting (interview study). Generating evidence from the three pillars altogether makes for a stronger approach to better research and tackle the local problem in this specific resource‐limited context, and address the implementation gaps.

Conclusions

This framework serves as a methodological roadmap to generate relevant evidence in similar resource‐limited contexts in low‐ and middle‐income countries, where there is a paucity of published studies in the literature about childhood cancer survival outcomes and resource use.
One‐Pot Synthesis of Diverse 1,4‐[60]Fullerephenols via Three‐Component Umpolung Cascade Coupling of Phenols, C60, and Nucleophiles
Authors: Zhang Jun‐Xiang , Wu Yuan‐Ze , Chen Dong‐Mei , Xuan Jun , Li Fei
Published: April 2023

A three‐component umpolung cascade coupling reaction of phenols, C60, and different nucleophiles which includes H2O, alcohols, triphenylamines and carbazoles was developed. Furthermore, one‐pot 1,4‐bisphenol coupling on C60 has been realized by this method. This practical protocol features high chemo‐ and regioselectivity, wide substrate range, easy operation and low cost, thus providing a robust method for the one‐pot synthesis of various unsymmetrical 1,4‐[60]fullerephenols.
Elucidating Conformational Dynamics and Thermostability of Designed Aromatic Clusters by Using Protein Cages
Authors: Hishikawa Yuki , Noya Hiroki , Nagatoishi Satoru , Yoshidome Takashi , Maity Basudev , Tsumoto Kouhei , Abe Satoshi , Ueno Takafumi
Published: April 2023

Multiple aromatic residues assemble to form higher ordered structures known as “aromatic clusters” in proteins and play essential roles in biological systems. However, the stabilization mechanism and dynamic behavior of aromatic clusters remain unclear. This study describes designed aromatic interactions confined within a protein cage to reveal how aromatic clusters affect protein stability. The crystal structures and calorimetric measurements indicate that the formation of inter‐subunit phenylalanine clusters enhance the interhelix interactions and increase the melting temperature. Theoretical calculations suggest that this is caused by the transformation of the T‐shaped geometry into π‐π stacking at high temperatures, and the hydration entropic gain. Thus, the isolated nanoenvironment in a protein cage allows reconstruction and detailed analysis of multiple clustering residues for elucidating the mechanisms of various biomolecular interactions in nature which can be applied to design of bionanomaterials.
Materials for Controlled Release of Local Anesthetics
Authors: Li Yang , Owens Gwen E. , Kohane Daniel S.
Published: April 2023

Controlled release systems for prolonged duration local anesthesia have long been an area of research interest, and now are entering clinical practice, in part driven by the opioid epidemic. We discuss the design considerations and material properties of systems for controlled release of local anesthetics, from relatively simple systems to covalent binding of drugs to materials and delivery triggered by external stimuli.
Interrelated Roles of Multiple Key Structure‐Directing Agents in Seed‐Mediated Growth of Monodisperse and Multibranched Au Nanoparticles
Authors: Zhao Xingjuan , Jia Yuechen , Wallace Gregory Q. , Bazuin C. Geraldine , Masson Jean‐Francois
Published: April 2023

Detailed mechanistic investigations of the interrelated roles of multiple key structure‐directing agents in the growth solution of Au nanoparticles (AuNPs) is required for the optimization of synthetic protocols. Here, we report a robust seed‐mediated growth strategy for synthesizing multibranched NPs (MB‐AuNPs) with monodispersed size distribution, and investigate the roles of Ag ions and 4‐(2‐hydroxyethyl)piperazine‐1‐ethanesulfonic acid (HEPES) based on an overgrowth synthesis approach. The intertwining roles of Ag+, surface‐capping stabilizers, and reducing agents were elucidated, and used to control the morphology of MB‐AuNPs. The overgrowth of MB‐AuNPs involves two distinct underlying pathways, namely, directional and anisotropic growth of Au branches on specific facets of Au seeds as well as an aggregation and growth mechanism governed by HEPES. In addition to Ag ions and HEPES, morphology tunability can also be achieved by pre‐modification of the Au seeds with molecular probes. Optimized probe‐containing MB‐AuNPs prove to be excellent surface‐enhanced Raman scattering (SERS) substrates and nanozymes. Taken together, the results of this work reveal the mechanistic evolution of nanocrystal growth which should stimulate the development of new synthetic strategies, improve the capabilities of tuning the optical, catalytic, and electronic properties of NPs, and further advance their applications in biolabeling, imaging, biosensing, and therapy.
He++N2 Charge Transfer Reaction: An Ab initio Analysis
Authors: Reja Deboki , Kumar Sanjay
Published: April 2023

An ab initio analysis on the involved potential energy surfaces is presented for the investigation of the charge transfer mechanism for the He++N2 system. At high collision energy, as many as seven low‐lying electronic states are observed to be involved in the charge transfer mechanism. Potential energy surfaces for these low‐lying electronic states have been computed in the Jacobi scattering coordinates, applying multireference configuration interaction level of theory and aug‐cc‐pVQZ basis sets. Asymptotes for the ground and various excited states are assigned to mark the entrance (He++N2) and charge transfer channels (He+N2+). Nonadiabatic coupling matrix elements and quasi‐diabatic potential energy surfaces have been computed for all seven states to rationalize the available experimental data on the charge transfer processes and to facilitate dynamics studies.
Second Harmonic Generation Signatures of Supramolecular Assemblies Based on Amide Moieties
Authors: Ramos Tárcius N. , Le Bras Laura , Dory Yves L. , Champagne Benoît
Published: April 2023

Targeting the use of the second harmonic generation (SHG) as a bioimaging technique to unravel the formation of aggregates, the SHG first hyperpolarizabilities (
) of assemblies of benzene‐1,3,5‐tricarboxamide derivatives have been evaluated at the density functional theory level. Calculations have revealed that i) the assemblies exhibit SHG responses and the total first hyperpolarizability responses of the aggregates are evolving with their size. The largest aggregation effect is a 18‐times increase for
of B4 when going from the monomer to the pentamer, that ii) the intrinsic SHG responses described by the hyper‐Rayleigh Scattering
are enhanced in presence of iodine atoms on the phenyl core, that iii) the side chains affect the relative orientation of the dipole moment and first hyperpolarizability vectors, which impacts more the EFISHG quantities than their moduli, and that iv) the radial component to
is dominant for the compounds having the largest responses. These results have been obtained using the sequential molecular dynamics then quantum mechanics approach to account for dynamic structural effects on the SHG responses.
Supramolecular Luminescent Nano‐assemblies Based on Macrocycles and Amphiphiles for Cell Imaging
Authors: Qian Nina , Hou Xiao‐Fang , Tang Yuqi , Zhang Shu , Chen Xu‐Man , Li Quan
Published: April 2023

Supramolecular luminescent nano‐assemblies for cell imaging have recently attracted increasing interest, not only because of their outstanding photophysical properties, but also because of their easy fabrication through supramolecular strategies, good biocompatibility, high stability to photo‐ and micro‐environments in cells, and facile combination of imaging and synergistic therapy for cancers. Luminescence‐based bioimaging has great advantages, such as high sensitivity, being non‐invasive, and functioning in real‐time, leading to its wide application in many fields, including disease research, drug research, cell markers, gene expression, gene function studies, and protein interaction. In this Review, recent progress in the application of macrocycle‐mediated (e.g., cyclodextrins, cucurbiturils, calixarenes, and pillar[n]arenes) and functionalized amphiphilic molecule‐based supramolecular luminescent nanoparticles in cell imaging, especially targeted cell imaging of specific organelles, is reviewed. The combination of imaging with drug delivery, gene delivery, and photodynamic therapy is also introduced.
Comparison of the impact of two types of removable partial dentures on the periodontal health of the remaining teeth: A prospective clinical study
Authors: Bukleta Manushaqe S. , Selmani Mimoza , Bukleta Dashnor
Published: April 2023

Objective

To evaluate and compare the impact of two removable partial dentures (acrylic removable partial denture [ARPD] and metallic removable partial denture [MRPD]) on periodontal tissues of the remaining teeth in the first 12 months of denture use.

Materials and Methods

This prospective clinical study included 40 patients, of which 20 received ARPDs, 20 received MRPDs, nine in the maxilla, and 11 in the mandible each. The patients were 45–65 years old; 24 were females, and 16 were males. Patients’ demographic details, clinical indicators of periodontal complications, and biochemical measurement of Hs‐C‐reactive protein (CRP) and alkaline phosphatase (ALP) were considered. One‐way analysis of covariance and Friedman were used to measure the differences in clinical periodontal parameters between the two types of dentures.

Results

The significant findings were: Plaque index (PLAQ) scores for abutment teeth were higher in MRPD wearers (mean = 12.15) than ARPD wearers (mean = 10.45), whereas ARPD users had significantly higher mean bleeding on probing (BOP) values (mean = 1.5) than MRPD users (mean = 0.00); mobility of abutment teeth showed no significant differences; timeline comparisons showed a significant increase in the percentage of nonabutment teeth mobility in ARPD users (p = .028) compared with MRPD users over the same follow‐up period (p = .102).

Conclusions

For a short‐term period of 1 year, periodontal and mobility parameters have no significant impact on the abutment and nonabutment teeth of ARPD and MRPD users. Moreover, biochemical markers (CRP and ALP) for periodontal inflammation exhibited no significant difference in both types of dentures.
How eco‐control systems enhance carbon performance via low‐carbon supply chain collaboration? The moderating role of organizational unlearning
Authors: Wei Shuochen , Wang Lifang , Jiang Wenbo , Feng Liwei , Feng Taiwen
Published: April 2023

Despite the increasing awareness of eco‐control systems (ECS), whether and how a firm's deployment of ECS affect carbon performance is not known. Drawing on organizational learning theory, this study investigates how a firm's implementation of ECS enhances carbon performance via low‐carbon supply chain collaboration, and examines the moderating effect of organizational unlearning. To verify these hypotheses, we conduct hierarchical regression analyses using survey data from 297 Chinese manufacturers. Our results indicate that both supplier and customer low‐carbon collaborations mediate the impact of ECS on carbon performance. In addition, organizational unlearning strengthens the impact of ECS on customer low‐carbon collaboration, but weakens the impact of ECS on supplier low‐carbon collaboration. This study extends the digital transition and sustainability literature by unpacking the “black box” of transforming ECS into carbon performance and considering the contingency role of organizational unlearning. Our findings provide managers with new digital technologies to improve low‐carbon supply chain management and guide governments to appropriately extend policies that accelerate the manufacturing industry's transition to sustainability.
O‐GlcNAcylated LARP1 positively regulated by circCLNS1A facilitates hepatoblastoma progression through DKK4/β‐catenin signalling
Authors: Cui Zhongqi , He Jiangtu , Zhu Jiabei , Ni Wenxuan , Liu Li , Bian Zhixuan , Mao Siwei , Gu Song , Shan Yuhua , Chu Zhexuan , Wu Qi , Lu Jiayi , Liu Ya , Sun Fenyong , Pan Qiuhui , Zhang Yue , Huang Nan , Ma Ji
Published: April 2023

Background

Accumulating studies have shown that La‐related protein 1 (LARP1) is involved in the occurrence and development of various tumours. However, the expression pattern and biological role of LARP1 in hepatoblastoma (HB) remain unclear so far.

Methods

LARP1 expression level in HB and adjacent normal liver tissues was analysed by qRT‐PCR, Western blotting and immunohistochemistry assays. The prognostic significance of LARP1 was evaluated by Kaplan–Meier method and multivariate Cox regression analysis. In vitro and in vivo functional assays were implemented to clarify the biological effects of LARP1 on HB cells. Mechanistically, the regulatory roles of O‐GlcNAcylation and circCLNS1A in LARP1 expression were investigated by co‐immunoprecipitation (co‐IP), immunofluorescence, RNA immunoprecipitation (RIP), RNA pull‐down and protein stability assays. Moreover, RNA‐sequencing, co‐IP, RIP, mRNA stability and poly(A)‐tail length assays were performed to investigate the association between LARP1 and DKK4. The expression and diagnostic significance of plasma DKK4 protein in multi‐centre cohorts were evaluated by ELISA and ROC curves.

Results

LARP1 mRNA and protein levels were remarkably elevated in HB tissues and associated with worse prognosis of HB patients. LARP1 knockdown abolished cell proliferation, triggered cell apoptosis in vitro as well as prohibited tumour growth in vivo, whereas LARP1 overexpression incited HB progression. Mechanistically, O‐GlcNAcylation of LARP1 Ser672 by O‐GlcNAc transferase strengthened its binding to circCLNS1A and then protected LARP1 from TRIM‐25‐mediated ubiquitination and proteolysis. LARP1 upregulation subsequently led to DKK4 mRNA stabilisation by competitively interacting with PABPC1 to prevent DKK4 mRNA from B‐cell translocation gene 2‐dependent deadenylation and degradation, thus facilitating β‐catenin protein expression and nuclear import.

Conclusion

This study indicates that upregulated protein level of O‐GlcNAcylated LARP1 mediated by circCLNS1A promotes the tumorigenesis and progression of HB through LARP1/DKK4/β‐catenin axis. Hence, LARP1 and DKK4 are promising therapeutical target and diagnostic/prognostic plasma biomarker for HB.
Diaryl ether derivative inhibits GPX4 expression levels to induce ferroptosis in thyroid cancer cells
Authors: Pamarthy Deepika , Behera Santosh Kumar , Swain Sonam , Yadav Sanjay , Suresh Surisetti , Jain Nishant , Bhadra Manika Pal
Published: April 2023

Papillary thyroid carcinoma contributes to about 80% of the total thyroid cancer cases. BRAFV600E is a frequently occurring mutation in PTCs. Although several BRAF inhibitors are available, many thyroid cancer patients acquire resistance to BRAF inhibitors. Therefore, new targets and drugs need to be identified as therapies. Ferroptosis is a recently discovered type of cell death, and inhibiting glutathione peroxidase 4 (GPX4) using small molecules was found to trigger ferroptosis. But it is unknown whether inhibiting GPX4 renders thyroid cancer cells susceptible to ferroptosis. To identify novel GPX4 inhibitors, we focused on our previously reported cohort of diaryl ether and dibenzoxepine molecules. In this study, we asked whether diaryl ether and dibenzoxepine derivatives trigger ferroptosis in thyroid cancer cells. To answer this question, we screened diaryl ether and dibenzoxepine derivatives in cell‐based assays and performed mechanism of action studies. We found that a diaryl ether derivative, 16 decreased thyroid cell proliferation and triggered ferroptosis by inhibiting GPX4 expression levels. Molecular modeling and dynamics simulations showed that 16 binds to the active site of GPX4. Upon deciphering the mode of 16‐induced ferroptosis, we found that 16 treatments decrease mitochondrial polarization and reduce mitochondrial respiration similar to a ferroptosis inducer, RSL3. We conclude that the diaryl ether derivative, 16 inhibits GPX4 expression levels to induce ferroptosis in thyroid cancer cells. Based on our observations, we suggest that 16 can be lead‐optimized and developed as a ferroptosis‐inducing agent to treat thyroid cancers.
Berberine targets KIF20A and CCNE2 to inhibit the progression of nonsmall cell lung cancer via the PI3K/AKT pathway
Authors: Wang Qi , Wu Hua , Wu Qingquan , Zhong Sheng
Published: April 2023

Background

Nonsmall cell lung cancer (NSCLC) is the main type of lung cancer, accounting for approximately 85%. Berberine (BBR), a commonly used traditional Chinese medicine, has been reported to exhibit a potential antitumor effect in various cancers. In this research, we explored the function of BBR and its underlying mechanisms in the development of NSCLC.

Methods

Cell Counting Kit‐8 (CCK‐8), 5‐ethynyl‐20‐deoxyuridine (EdU), colony formation assays, flow cytometry, and transwell invasion assay were employed to determine cell growth, the apoptotic rate, cell invasion of NSCLC cells, respectively. Western blot was applied for detecting the protein expression of c‐Myc, matrix metalloprotease 9 (MMP9), kinesin family member 20A (KIF20A), cyclin E2 (CCNE2), and phosphatidylinositol‐3‐kinase/protein kinase B (PI3K/AKT) pathway‐related proteins. Glycolysis was evaluated by detecting glucose consumption, lactate production, and adenosine triphosphate/adenosine diphosphate (ATP/ADP) ratio with the matched kits. Real‐time quantitative polymerase chain reaction (RT‐qPCR) was conducted to analyze the level of KIF20A and CCNE2. Tumor model was established to evaluate the function of BBR on tumor growth in NSCLC in vivo. In addition, immunohistochemistry assay was employed to detect the level of KIF20A, CCNE2, c‐Myc, and MMP9 in mice tissues.

Results

BBR exhibited suppressive effects on the progression of NSCLC, as evidenced by inhibiting cell growth, invasion, glycolysis, and facilitating cell apoptosis in H1299 and A549 cells. KIF20A and CCNE2 were upregulated in NSCLC tissues and cells. Moreover, BBR treatment significantly decreased the expression of KIF20A and CCNE2. KIF20A or CCNE2 downregulation could repress cell proliferation, invasion, glycolysis, and induce cell apoptosis in both H1299 and A549 cells. The inhibition effects of BBR treatment on cell proliferation, invasion, glycolysis, and promotion effect on cell apoptosis were rescued by KIF20A or CCNE2 overexpression in NSCLC cells. The inactivation of PI3K/AKT pathway caused by BBR treatment in H1299 and A549 cells was restored by KIF20A or CCNE2 upregulation. In vivo experiments also demonstrated that BBR treatment could repress tumor growth by regulating KIF20A and CCNE2 and inactivating the PI3K/AKT pathway.

Conclusion

BBR treatment showed the suppressive impact on the progression of NSCLC by targeting KIF20A and CCNE2, thereby inhibiting the activation of the PI3K/AKT pathway.
Lateral variations in the signature of earthquake‐generated deposits in Lake Iznik, NW Turkey
Authors: Gastineau R. , Sabatier P. , Fabbri S. C. , Anselmetti F. S. , Roeser P. , Findling N. , Şahin M. , Gündüz S. , Arnaud F. , Franz S. O. , Ünsal N. D. , de Sigoyer J.
Published: April 2023

Using lake‐sediment cores to document past seismicity requires a comprehensive understanding of possible lateral variations in depositional processes. This study aims to reveal the lateral variations in earthquake‐induced event deposits throughout Lake Iznik, a large lake located on the middle strand of the North Anatolian Fault. Based on stratigraphic, sedimentological and geochemical analyses of 14 sediment cores from two subbasins across the lake, five different types of event deposits (T1–T5) were identified and characterised. One event deposit type (T5) is restricted to a delta mouth, characterised by the occurrence of authigenic Fe‐Mn carbonates and interpreted to result from flood events. The four other types of event deposits are characterised by their synchronicity between cores and their age consistency with historical earthquakes and are interpreted to be likely generated by earthquakes. The locally prominent 1065 CE historical earthquake that ruptured the sub‐lacustrine Iznik Fault produced at least three different types of event deposits. One deposit type (T2) is only observed for this very local earthquake, implying that the type of event deposit might also depend on ground‐motion parameters. At the lake scale, the occurrence of various event deposits depends on the flow distance from the source of sediment destabilisations to the coring site.
Revalidation and expanded description ofMustela aistoodonnivalis(Mustelidae: Carnivora) based on a multigene phylogeny and morphology
Authors: Liu Yingxun , Pu Yingting , Chen Shunde , Wang Xuming , Murphy Robert W. , Wang Xin , Liao Rui , Tang Keyi , Yue Bisong , Liu Shaoying
Published: April 2023

The lacked‐teeth pygmy weasel,Mustela aistoodonnivalisWu & Kao, 1991, was originally described as being from Taibai Mountain and Zhashui county, Shaanxi, China. Subsequently, it was considered a subspecies or synonym ofMustela nivalis. In a faunal survey of northwestern Sichuan, eight specimens ofM. aistoodonnivaliswere collected. A molecular phylogenetic analysis of one mitochondrial and six nuclear genes clustered the specimens as a distinct clade and not withM. nivalis. Morphologically, the lack of the second lower molar differentiated them fromM. nivalis, and genetic distances were typical of discrete species. These analyses confirmed thatM. aistoodonnivalisis an independent species in the genusMustela.
Elevation and phylogeny shape herbaceous seed dormancy in a biodiversity hotspot of southwest China
Authors: Chen Kai , Chen Zi‐Hong , Huang Yuan‐Yuan , Jiang Zhong‐Hua
Published: April 2023

Seed dormancy contributes greatly to successful establishment and community stability and shows large variation over a continuous status scale in mountain ecosystems. Although empirical studies have shown that seed dormancy status (SDS) is shaped by elevation and phylogenetic history in mountain ecosystems, few studies have quantified their combined effects on SDS. Here, we collected mature seeds from 51 populations of 11 Impatiens species (Balsaminaceae) along an elevational gradient in the Gaoligong Mountains of southwest China and estimated SDS using mean dormancy percentage of fresh seeds germinated at three constant temperatures (15, 20, and 25°C). We downloaded 19 bioclimatic variables from WorldClim v.2.1 for each Impatiens population and used internal transcribed spacer (ITS), atpB‐rbcL, and trnL‐F molecular sequences from the GenBank nucleotide database to construct a phylogenetic tree of the 11 species of Impatiens. Logistic regression model analysis was performed to quantify the effects of phylogeny and environment on SDS. Results identified a significant phylogenetic SDS signal in the Impatiens species. Furthermore, elevation and phylogeny accounted for 63.629% of the total variation in SDS among the Impatiens populations. The best logistic model indicated that temperature was the main factor influencing variation in SDS among the Impatiens species, and model residuals were significantly correlated with phylogeny, but not with elevation. Our results indicated that seed dormancy is phylogenetically conserved, and climate drives elevational patterns of SDS variation in mountain ecosystems. This study provides new insights into the response of seed plant diversity to climate change.
A global meta‐analysis reveals contrasting impacts of air, light, and noise pollution on pollination
Authors: Guenat Solène , Dallimer Martin
Published: April 2023

In the face of biodiversity decline, understanding the impact of anthropogenic disturbances on ecosystem functions is critical for mitigation. Elevated levels of pollution are a major threat to biodiversity, yet there is no synthesis of their impact on many of the major ecosystem functions, including pollination. This ecosystem function is both particularly vulnerable as it depends on the fine‐tuned interaction between plants and pollinators and hugely important as it underpins the flora of most habitats as well as food production. Here, we untangle the impact of air, light, and noise pollution on the pollination system by systematically evaluating and synthesizing the published evidence via a meta‐analysis. We identified 58 peer‐reviewed articles from three databases. Mixed‐effects meta‐regression models indicated that air pollution negatively impacts pollination. However, there was no effect of light pollution, despite previous studies that concentrated solely on pollinators suggesting a negative impact. Evidence for noise pollution was extremely limited. Unless action is taken to tackle air pollution, the capacity to support well‐functioning diverse pollination systems will be compromised, with negative consequences for habitat conservation and food security.
Detecting ecological traps inhuman‐alteredlandscapes: A case study of the thick‐billed longspur nesting in croplands
Authors: Swicegood Amber E. , Ellison Kevin S. , Sather Marisa , Somershoe Scott G. , McNew Lance B.
Published: April 2023

Conversion of the North American prairies to cropland remains a prominent threat to grassland bird populations. Yet, a few species nest in these vastly modified systems. Thick‐billed longspurs historically nested in recently disturbed or sparsely vegetated patches within native mixed‐grass prairie, but observations of longspurs in spring cereal and pulse crop fields during the breeding season in northeastern Montana, USA, suggest such fields also provide cues for habitat selection. Maladaptive selection for poor‐quality habitat may contribute to ongoing declines in longspur populations, but information on thick‐billed longspur breeding ecology in crop fields is lacking. We hypothesized that crop fields may function as ecological traps; specifically, we expected that crop fields may provide cues for territory selection, but frequent human disturbance would result in reduced reproduction. To address this hypothesis, we compared measures of habitat selection (settlement patterns and trends in abundance) and productivity (nest density, nest survival, and number of young fledged) between crop fields and native grassland sites during 2020–2021. Across both years, settlement patterns were similar between site types and occupancy ranged from 0.52 ± 0.17 SE to 0.99 ± 0.01 on April 7 and 30, respectively. Early season abundance differed by year, and changes in abundance during the breeding season appeared to be associated with precipitation‐driven vegetation conditions rather than habitat type. While an index of nest density was lower in crop than native sites, the number of young fledged per successful nest (2.9 ± 0.18 SE) and nest survival (0.24 ± 0.03 SE;n = 222 nests) were similar for crop and native sites. Collectively, the data did not support our ecological trap hypothesis: longspurs did not exhibit a clear preference for crop sites and reproductive output was not significantly reduced. Our results indicate that croplands may provide alternative breeding habitat within a human‐dominated landscape.
Post‐glacial colonization of the Fennoscandian coast by a plant parasitic insect with an unusual life history
Authors: Solbreck Christer , Cassel‐Lundhagen Anna , Laugen Ane T. , Kaňuch Peter
Published: April 2023

Species that exhibit very peculiar ecological traits combined with limited dispersal ability pose a challenge to our understanding of ecological and evolutionary mechanisms. This is especially true when they have managed to spread over long distances, overcome physical barriers, and colonize large areas. Climate and landscape changes, trophic web relations, as well as life history all interact to shape migration routes and present‐day species distributions and their population genetic structures. Here we analyzed the post‐glacial colonization of northern Europe by the gall midge Contarinia vincetoxici, which is a monophagous parasite on the perennial herb White swallowwort (Vincetoxicum hirundinaria). This insect not only has a narrow feeding niche but also limited dispersal ability and an exceptionally long dormancy. Gall midge larvae (n = 329) were collected from 16 sites along its distribution range in Denmark, Sweden, and Finland. Using microsatellite loci and knowledge of the species and the regions' history, we investigated the role of landscape change, host plant distribution, insect population dynamics, and life history in shaping the population genetic structure of the insect. We devoted particular interest to the role of the insect's presumed poor dispersal capacity in combination with its exceptionally extended diapause. We found significant levels of local inbreeding (95% highest posterior density interval = 0.42–0.47), low‐level within‐population heterozygosity (mean HE = 0.45, range 0.20–0.61) with private alleles in all populations except two. We also found significant (p < .001) regional isolation‐by‐distance patterns, suggesting regularly recurring mainly short‐distance dispersal. According to approximate Bayesian computations, C. vincetoxici appears to have colonized the study area via wind‐aided flights from remote areas approximately 4600–700 years before present when the land has gradually risen above the sea level. Extremely long dormancy periods have allowed the species to “disperse in time”, thereby aiding population persistence despite generally low census population sizes.
Causal mechanisms for negative impacts of energy development inform management triggers for sagebrush birds
Authors: Latif Quresh S. , Van Lanen Nicholas J. , Chabot Eric J. , Pavlacky David C.
Published: April 2023

Estimated population trends can identify declining species to focus biological conservation, but monitoring may fail to illuminate causes of population change and strategies for reversing declines. Monitoring programs can relate trends with environmental attributes to test causal hypotheses, but typical analytical approaches do not explicitly support causal inference, diluting available data for informing conservation. The U.S. Bureau of Land Management (BLM) extended Integrated Monitoring in Bird Conservation Regions with a quasi‐experimental sampling design over a 10‐year period (2010–2019) to evaluate the impacts of oil and gas development on sagebrush birds within the Atlantic Rim Natural Gas Field Development Project in southern Wyoming. We analyzed resulting data using a multiscale community occupancy model to estimate trends in species occupancy and richness relevant to management triggers. Additionally, we employed path analysis to evaluate mechanisms underlying observed trends to inform potential management responses. Fine‐scale occupancy for sage thrasher (Oreoscoptes montanus) declined within the high‐development stratum at a rate sufficient to meet an a priori management trigger established by the BLM. Two additional sagebrush‐associated species, Brewer's (Spizella breweri) and sagebrush sparrow (Artemisiospiza nevadensis), exhibited negative development relationships with trend, as did overall species richness, and richness of grassland, sagebrush, and generalist guilds. We identified well pad density and invasive plants associated with energy development as causal factors contributing to these negative development impacts. We demonstrate an analytical approach for both estimating occupancy trends and identifying underlying causes to inform conservation action. Reducing the development footprint, including well pad density and associated invasive plants, could help reduce or limit impacts on birds within this landscape.
Biological and Catalytic Applications of Pd(II)‐Indenyl Complexes Bearing Phosphine andN‐Heterocyclic Carbene Ligands
Authors: Bortolamiol Enrica , Isetta Giacomo , Caligiuri Isabella , Demitri Nicola , Paganelli Stefano , Rizzolio Flavio , Scattolin Thomas , Visentin Fabiano
Published: April 2023

A general synthetic entryway into novel cationic Pd(II) indenyl complexes bearing one alkyl/aryl phosphine and oneN‐heterocyclic carbene is reported. All metal complexes have been exhaustively characterized by spectroscopic and structural analyses, highlighting that the indenyl fragment has an hapticity intermediate between η3and η5. Most of the target complexes are stable in solid state and in solution for a long time. Two different applications of these organopalladium compounds are proposed. Firstly, they have been tested as antiproliferative agents towards three different ovarian cancer cell lines, showing a cytotoxicity significantly higher than that of cisplatin, with a clear dependence on the nature of the coordinated phosphine. Moreover, the similar cytotoxicity towards cisplatin‐sensitive and cisplatin‐resistant cell lines suggests that these new palladium derivatives act with a different mechanism of action with respect to classical platinum‐based drugs.

Finally, the water‐soluble palladium complexes bearing 1,3,5‐triaza‐7‐phosphaadamantane (PTA) have demonstrated interesting catalytic performances in Suzuki–Miyaura coupling in aqueous media, being, inter alia, readily and efficiently recyclable.
Synthesis and Transition Metal Complexes of ((Phenylphosphanediyl) bis(ethyne‐2,1‐diyl))bis(diphenyl‐phosphane), [PhP{C≡CPPh2}2]
Authors: Mondal Dipanjan , Kumar Rajnish , Mohite Manali A. , Balakrishna Maravanji S.
Published: April 2023

This paper describes the synthesis of a new acetylene‐bridged triphosphine, ((phenylphosphanediyl)bis‐(ethyne‐2,1‐diyl))bis(diphenylphosphane) [PhP{C≡CPPh2}2] (2) and its coordination complexes of RuII, RhIII, CuI, PdII and PtII. The reaction of diethynylphenylphosphine [PhP{C≡CH}2] (1) with two equivalents of LiHMDS followed by the addition of PPh2Cl resulted in 2. Treatment of 2 with [Ru(η6‐p‐cymene)Cl2]2 and [RhCp*Cl2]2 in 1 : 1.5 molar ratios produced trinuclear complexes [{Ru(η6‐p‐cymene)Cl2}3{μ3‐PPh(C≡CPPh2)2}] (3) and [(RhCp*Cl2)3{μ3‐PPh(C≡CPPh2)2}] (4). The molecular structure of 3 was confirmed by single crystal X‐ray analysis. Treatment of 2 with M(COD)Cl2 (M=Pd, Pt) in 2 : 3 ratio afforded open book type complexes [(MCl2)3{μ3‐PPh(C≡CPPh2)}2] (5 M=Pd, 6 M=Pt). The reaction of 2 with CuI in 1 : 2 ratio afforded 1‐D coordination polymer [{Cu2(μ2‐I)2(CH3CN)}{PPh(C≡CPPh2)2}3{CuI}2] (7) containing [(CuI)2{μ2‐(P−C≡C−P)3}] cylindrical units.
The Remarkably Robust, Photoactive Tungsten Iodide Cluster [W6I12(NCC6H5)2]
Authors: Pachel Florian , Ströbele Markus , Romao Carl P. , Enseling David , Jüstel Thomas , Meyer Hans‐Jürgen
Published: April 2023

The new heteroleptic tungsten iodide cluster compound [W6I12(NCC6H5)2] is presented. The synthesis is carried‐out from Cs2W6I14 and ZnI2 under solvothermal conditions in benzonitrile solution, yielding red cube‐shaped crystals. [W6I12(NCC6H5)2] represents a heteroleptic [W6I8]‐type cluster bearing four apical iodides and two benzonitrile ligands. Molecular [W6I12(NCC6H5)2] clusters form a robust hydrogen bridged crystal structure with high thermal stability and high resistibility against hydrolysis. The electronic structure is analyzed by quantum chemical methods of the calculated electron localization function (ELF) and the band structure. Photoluminescence measurements are performed to verify and describe the photophysical properties of [W6I12(NCC6H5)2]. Finally, the photocatalytic properties of [W6I12(NCC6H5)2] are evaluated as a proof‐of‐concept.
Pyridine‐Stabilized Cationic Silanethione Tungsten Complexes: Synthesis, Structures, and Reactivity
Authors: Muraoka Takako , Ishizeki Ryosuke , Tanabe Shun , Ueno Keiji
Published: April 2023

Silanethione compounds, R2Si=S, have been recognized as highly reactive species. One reliable way to stabilize silanethione is its coordination to transition metal fragments to convert silanethione‐coordinated transition metal complexes. Herein, we report the synthesis, structure, and reactivity of a second cationic silanethione tungsten complex [Cp*(OC)3W{S=SiR2(py)}]TFPB (R=Me (5 a), Ph (5 b), Cp*: η5‐C5Me5, py: pyridine, and TFPB−: [B{3,5‐(CF3)2C6H3}4]−). Complex5was obtained by H−abstraction from the Si atom in the corresponding silylsulfanyl complex Cp*(OC)3W(SSiR2H) (4) with Ph3CTFPB, followed by the addition of pyridine. The reaction of5with PhNCS and PMe3produced [Cp*(OC)3W{SSiR2N(Ph)C(PMe3)2}]TFPB (R=Me (6 a), Ph (6 b)) via the elimination of pyridine and the addition of the 1,3‐dipolar species PhNC(PMe3)2(A) to the Si atom.
Palladium(II) Complexes of 1‐Phosphaisoprene Molecules and Polymers: Reversible Cross‐Linking of a Phosphorus‐Containing Polymer
Authors: Walsgrove Henry T. G. , Chowdhury Khadiza (Rodella) K. , Dabringhaus Philipp , Patrick Brian O. , Gates Derek P.
Published: April 2023

The anionic polymerization of 1‐phosphaisoprene [Mes*P=C(Me)−CH=CH2 (E‐1)] affords poly(1‐phosphaisoprene) 2 in high yield (75 %). Concentrated solutions of polymer 2 (Mn=21,800 g mol−1; Đ=1.02) a P‐analogue of natural rubber, undergo gelation upon treatment with [Pd(cod)Cl2] (0.15 P equiv). Evidence for P‐coordination of 2 to PdII was obtained by 31P and 1H NMR spectroscopy. The gelation is reversed by the addition of PMe3 and the reformation of recoverable 2 along with [PdII−PMe3] complexes were confirmed by 31P NMR spectroscopy. The use of labile metal‐ligand bonds to reversibly form gels is unprecedented and has relevance to self‐healing materials. In contrast, coordination of 2 to [Pd(η3‐C3H5)(μ‐Cl)]2 affords the well‐defined complex 2 ⋅ [Pd(η3‐C3H5)Cl] which was characterized by 31P, 1H, 13C{1H} NMR spectroscopy and GPC. This polymer chemistry was complemented by detailed molecular model studies of the coordination chemistry of monomer 1‐phosphaisoprene E‐1 with [Pd(cod)Cl2] and [Pd(η3‐C3H5)(μ‐Cl)]2].
Lithiation and Alkylation of the Imidazole Backbone
Authors: Lundevall Frida Johanne , Bjørsvik Hans‐René
Published: April 2023

A concise improved method for the alkylation of the imidazole backbone has been developed. The positions 1 and 2 of the imidazole ring were protected with tetrahydro‐2H‐pyran‐2‐yl and chloro groups, respectively. Position 5 of imidazole was then lithiated, whereupon alkylation could be conducted by means of a variety of electrophilic reagents including haloalkanes, aldehydes, and ketones. Finally, the two protective / auxiliary groups on the positions 1 and 2 were easily removed by means of treatment with acid and base and hydrogenation, respectively. The developed method proved good functional group tolerance but demanded non‐bulky molecular moieties in the vicinity of the attaching C‐atom of the reagent. The novel alkylating method was used to synthesize two new NHC−Ag complexes holding branched alkyl groups on the imidazole backbone.
A simulation model of climate policy analysis for sustainable environment in Pakistan
Authors: Raza Muhammad Amir , Aman M. M. , Abro Abdul Ghani , Shahid Muhammad , Ara Darakhshan , Waseer Tufail Ahmed , Tunio Nadeem Ahmed , Soomro Shakir Ali , Jumani Touqeer Ahmed , Haider Raza
Published: April 2023

This study suggested a plan for making low carbon society (LCS) in Pakistan by 2050. Low Emissions Analysis Platform is used for simulation the entire energy system and forecasted the future CO2 emissions in relation to the use of renewable and fossil fuel resources under the two scenarios namely high carbon society (HCS) and LCS. Additionally, marginal abatement cost of future energy system is forecasted for the study period 2022–2050. The results revealed that, 100% de‐carbonization is possible under the LCS scenario. Further, this scenario suggested that 1123.15 TWh units of green energy are generated to meet the total energy demand of 966.05 TWh till 2050. Biomass has greater share of 380.16 TWh followed by wind 370.67 TWh, solar 358.74 TWh, and hydro 13.58 TWh respectively. CO2 emissions are reduced from 151.63 million metric tons in HCS scenario to 8.90 million metric tons in LCS scenario till 2050 but cost is increased from 46.36 billion US dollar in HCS scenario to 546.49 billion US dollar in LCS scenario for the year 2050. The technique can also be applicable to the developing, under‐developed and developed nations around the globe.