bluuebunny/crossref_metadata_2025 huggingface dataset:
Uneasy Pursuit: A Screenplay Exploring an Untreated Schizophrenia and Its Impacts on One’s Life
Authors: Faustina Ivana , Irawan Stefanny
Published: October 2022

Mental health has been overlooked in Indonesia for too long. Labels like ‘nuts’ and ‘insane’ are often associated with the matter, creating a stigma that undermines its significance. Therefore, this creative work intends to bring forth the urgency of mental health awareness, especially on women who are more prone to mental illness than men. The chosen topic is schizophrenia, which can result in fatal impacts, including suicide, if left untreated. The story follows Sandra, an Indonesian female police detective who unknowingly is battling schizophrenia while trying to catch a skilled mysterious criminal. After a series of regressions, she grows more miserable, reaches peak devastation when struck by grief, and tries to end her life. However, she manages to overcome the pain and, with the help of proper treatment, puts the illness under control. Conclusively, this work aims to highlight the importance of early treatment and awareness of mental illnesses.
Distribution of Abatement Funds Arising From US Opioid Litigation
Authors: Alexander G. Caleb , Mansour Omar
Published: October 2022

This Viewpoint discusses the settlement agreements reached against several major pharmaceutical distributors resulting from the US opioid epidemic and how those funds will be distributed amongst the states.
Association Between State-Issued COVID-19 Vaccine Mandates and Vaccine Administration Rates in 12 US States and the District of Columbia
Authors: Howard-Williams Mara , Soelaeman Rieza H. , Fischer Leah S. , McCord Russell , Davison Robin , Dunphy Christopher
Published: October 2022

Importance

Some US states have issued COVID-19 vaccine mandates; however, the association of these mandates with vaccination rates remains unknown.

Objective

To examine the association between announcing state-issued COVID-19 vaccine mandates that did not provide a test-out option for workers and the vaccine administration rates in terms of state-level first-dose vaccine administration and series completion coverage.

Design, Setting, and Participants

This cross-sectional study used publicly available, state-level aggregated panel data to fit linear regression models with 2-way fixed effects (state and time) estimating vaccine coverage changes 8 weeks before and 8 weeks after a state-issued COVID-19 vaccine mandate was announced. Mandates were announced on or after July 26, 2021, and were included only if they went into effect before December 31, 2021. Data were included from 13 state-level jurisdictions with a vaccine mandate in effect as of December 31, 2021, that did not allow recurring testing in lieu of vaccination (mandate group), and 14 state-level jurisdictions that allowed a test-out option and/or did not restrict vaccine requirements (comparison group).

Interventions/Exposures

The event of interest was the announcement of a state-issued COVID-19 vaccine mandate applicable to specific groups of workers.

Main Outcomes and Measures

The outcome measures were state-level daily COVID-19 vaccine first-dose administration and series completion coverage, reported as mean percentage point changes.

Results

Of 5 508 539 first-dose administrations in the 8-week postannouncement period, an estimated 634 831 (11.5%) were associated with the mandate announcement. First-dose administration coverage among 13 jurisdictions increased starting at 3 weeks after the mandate announcement, with statistically significant differences of 0.20, 0.33, 0.39, 0.45, 0.49, and 0.59 percentage points higher than the referent category coverage of 62.9%. Increases in vaccine series completion coverage were observed from 5 to 8 weeks after the announcement, but statistically significant differences from the referent category coverage of 56.3% were observed only during weeks 7 and 8 after the announcement (both differed by 0.2 percentage points; P = .05 and P = .02, respectively).

Conclusions and Relevance

The findings of this cross-sectional event study suggest that the announcement of state-issued vaccine mandates may be associated with short-term increases in vaccine uptake. This observed association may be a product of both a direct outcome experienced by groups governed by the mandate as well as the spillover outcome due to a government signaling the importance of vaccination to the general population of the state.
Trends in Racial and Ethnic Disparities in Barriers to Timely Medical Care Among Adults in the US, 1999 to 2018
Authors: Caraballo César , Ndumele Chima D. , Roy Brita , Lu Yuan , Riley Carley , Herrin Jeph , Krumholz Harlan M.
Published: October 2022

Importance

Racial and ethnic disparities in delayed medical care for reasons that are not directly associated with the cost of care remain understudied.

Objective

To describe trends in racial and ethnic disparities in barriers to timely medical care among adults during a recent 20-year period.

Design, Setting, and Participants

This was a serial cross-sectional study of 590 603 noninstitutionalized adults in the US using data from the National Health Interview Survey from 1999 to 2018. Data analyses were performed from December 2021 through August 2022.

Exposures

Self-reported race, ethnicity, household income, and sex.

Main Outcomes and Measures

Temporal trends in disparities regarding 5 specific barriers to timely medical care: inability to get through by telephone, no appointment available soon enough, long waiting times, inconvenient office or clinic hours, and lack of transportation.

Results

The study cohort comprised 590 603 adult respondents (mean [SE] age, 46.00 [0.07] years; 329 638 [51.9%] female; 27 447 [4.7%] Asian, 83 929 [11.8%] Black, 98 692 [13.8%] Hispanic/Latino, and 380 535 [69.7%] White). In 1999, the proportion of each race and ethnicity group reporting any of the 5 barriers to timely medical care was 7.3% among the Asian group; 6.9%, Black; 7.9%, Hispanic/Latino; and 7.0%, White (P > .05 for each difference compared with White individuals). From 1999 to 2018, this proportion increased across all 4 race and ethnicity groups (by 5.7, 8.0, 8.1, and 5.9 percentage points [pp] among Asian, Black, Hispanic/Latino, and White individuals, respectively; P < .001 for each), slightly increasing the disparities between groups. In 2018, compared with White individuals, the proportion reporting any barrier was 2.1 and 3.1 pp higher among Black and Hispanic/Latino individuals (P = .03 and P = .001, respectively). There was no significant difference in prevalence between Asian and White individuals. There was a significant increase in the difference in prevalence between Black individuals and White individuals who reported delaying care because of long waiting times at the clinic or medical office and because of a lack of transportation (1.5 pp and 1.8 pp; P = .03 and P = .01, respectively). In addition, the difference in prevalence between Hispanic/Latino and White individuals who reported delaying care because of long waiting times increased significantly (2.6 pp; P < .001).

Conclusions and Relevance

The findings of this serial cross-sectional study of data from the National Health Interview Survey suggest that barriers to timely medical care in the US increased for all population groups from 1999 to 2018, with associated increases in disparities among race and ethnicity groups. Interventions beyond those currently implemented are needed to improve access to medical care and to eliminate disparities among race and ethnicity groups.
Analysis of tripartite Synaptotagmin‐1‐SNARE‐complexin‐1 complexes in solution
Authors: Jaczynska Klaudia , Esquivies Luis , Pfuetzner Richard A. , Alten Baris , Brewer Kyle D. , Zhou Qiangjun , Kavalali Ege T. , Brunger Axel T. , Rizo Josep
Published: October 2022

Characterizing interactions of Synaptotagmin‐1 with the SNARE complex is crucial to understand the mechanism of neurotransmitter release. X‐ray crystallography revealed how the Synaptotagmin‐1 C2B domain binds to the SNARE complex through a so‐called primary interface and to a complexin‐1‐SNARE complex through a so‐called tripartite interface. Mutagenesis and electrophysiology supported the functional relevance of both interfaces, and extensive additional data validated the primary interface. However, ITC evidence suggesting that binding via the tripartite interface occurs in solution was called into question by subsequent NMR data. Here, we describe joint efforts to address this apparent contradiction. Using the same ITC approach with the same C2B domain mutant used previously (C2BKA‐Q) but including ion exchange chromatography to purify it, which is crucial to remove polyacidic contaminants, we were unable to observe the substantial endothermic ITC signal that was previously attributed to binding of this mutant to the complexin‐1‐SNARE complex through the tripartite interface. We were also unable to detect substantial populations of the tripartite interface in NMR analyses of the ITC samples or in measurements of paramagnetic relaxation effects, despite the high sensitivity of this method to detect weak protein complexes. However, these experiments do not rule out the possibility of very low affinity (KD > 1 mm) binding through this interface. These results emphasize the need to develop methods to characterize the structure of synaptotagmin‐1‐SNARE complexes between two membranes and to perform further structure–function analyses to establish the physiological relevance of the tripartite interface.
Changes in ambulance departures for assault calls during COVID‐19 pandemic restrictions
Authors: Pisl Vojtech , Vevera Jan , Štěpánek Lubomír , Volavka Jan
Published: October 2022

Restrictions related to COVID‐19 changed the daily behavior of people, including the expression of violence. Although an increased incidence of violent behavior, especially domestic violence, was expected during the pandemic, retrospective analyses have yielded mixed results. Records of ambulance departures to address injuries caused by assaults in the Pilsen region, Czech Republic, during the restrictive measures during the national state of emergency were compared to data from 3 previous years using general linear models. The number and severity of assaults were analyzed for the whole sample and separately for patients of either sex, for residential or nonresidential locations, and for domestic violence. Controlling for the seasonal effects, the number of assaults decreased by 39% during the pandemic restrictions compared to the 3 previous years. No difference was found between the effects of restrictions on assaults resulting in an injury of a male or female patient. The decrease was specifically pronounced in the sample of assaults in nonresidential locations, while no effect of restrictions was observed in assaults in residential locations and domestic assaults. Pandemic restrictions were associated with a decreased incidence of violent assaults that required ambulance services. Although the incidence decreased especially in those assaulted outside of their homes, we found no support for an increase in domestic violence or violence against women. Pandemic restrictions may have served as a protective rather than a risk factor for assaults severe enough to warrant a call for ambulance services.
Hybrid Block Copolymer/Perovskite Heterointerfaces for Efficient Solar Cells
Authors: Sun Jianguo , Li Bin , Hu Long , Guo Junjun , Ling Xufeng , Zhang Xuliang , Zhang Chi , Wu Xianxin , Huang Hehe , Han Chenxu , Liu Xinfeng , Li Youyong , Huang Shujuan , Wu Tom , Yuan Jianyu , Ma Wanli
Published: October 2022

Solution processable semiconductors like organics and emerging lead halide perovskites (LHPs) are ideal candidates for photovoltaics combining high performance and flexibility with reduced manufacturing cost. Moreover, the study of hybrid semiconductors would lead to advanced structures and deep understanding that will propel this field even further. Herein, a novel device architecture involving block copolymer/perovskite hybrid bulk heterointerfaces is investigated, such a modification could enhance light absorption, create an energy level cascade, and provides a thin hydrophobic layer, thus enabling enhanced carrier generation, promoting energy transfer and preventing moisture invasion, respectively. The resulting hybrid block copolymer/perovskite solar cell exhibits a champion efficiency of 24.07% for 0.0725 cm2‐sized devices and 21.44% for 1 cm2‐sized devices, respectively, together with enhanced stability, which is among the highest reports of organic/perovskite hybrid devices. More importantly, this approach has been effectively extended to other LHPs with different chemical compositions like MAPbI3 and CsPbI3, which may shed light on the design of highly efficient block copolymer/perovskite hybrid materials and architectures that would overcome current limitations for realistic application exploration.
Lanthanide(III)‐Cu4I4 Organic Framework Scintillators Sensitized by Cluster‐Based Antenna for High‐Resolution X‐ray Imaging
Authors: Liu Xiangmei , Li Ruhua , Xu Xueli , Jiang Yangyang , Zhu Wenjuan , Yao Yu , Li Feiyang , Tao Xiaofang , Liu Shujuan , Huang Wei , Zhao Qiang
Published: October 2022

Scintillator‐based X‐ray imaging has attracted great attention from industrial quality inspection and security to medical diagnostics. Herein, a series of lanthanide(III)‐Cu4I4 heterometallic organic frameworks (Ln‐Cu4I4 MOFs)‐based X‐ray scintillators are developed by rationally assembling X‐ray absorption centers ([Cu4I4] clusters) and luminescent chromophores (Ln(III) ions) in a specific manner. Under X‐ray irradiation, the heavy inorganic units ([Cu4I4] clusters) absorb the X‐ray energy to populate triplet excitons via halide‐to‐ligand charge transfer (XLCT) combined with the metal‐to‐ligand charge‐transfer (MLCT) state (defined as the X/MLCT state), and then the 3X/MLCT excited state sensitizes Tb3+ for intense X‐ray‐excited luminescence via excitation energy transfer. The obtained Tb‐Cu4I4 MOF scintillators exhibit high resistance to humidity and radiation, excellent linear response to X‐ray dose rate, and high X‐ray relative light yield of 29 379 ± 3000 photons MeV−1. The relative light yield of Tb‐Cu4I4 MOFs is ≈3 times higher than that of the control Tb(III) complex. X‐ray imaging tests show that the Tb‐Cu4I4 MOFs‐based flexible scintillator film exhibits a high spatial resolution of 12.6 lp mm−1. These findings not only provide a promising design strategy to develop lanthanide‐MOF‐based scintillators with excellent scintillation performance, but also exhibit high‐resolution X‐ray imaging for biological specimens and electronic chips.
Nanomaterial‐Boosted Tumor Immunotherapy Through Natural Killer Cells
Authors: Zhan Mengsi , Guo Yunqi , Shen Mingwu , Shi Xiangyang
Published: October 2022

Natural killer (NK)‐cell immunotherapy as an alternative to T‐cell immunotherapy has been widely used in clinical cell immunotherapy of various tumors. Despite the surprising findings, the widespread applications of NK cells are still limited by the insufficient expansion and short lifespan of adoptive NK cells in vivo, the poor penetration of NK cells in solid tumors, as well as the immunosuppressive tumor microenvironment that may cause the inactivation of NK cells. Fortunately, the emergence of nanomaterials provides many opportunities to address these vexing problems, thus overcoming the barriers faced by NK cells and promoting the tumor inhibitory efficacy of NK cells. Herein, the recent advances in the rational design of nanomaterials for boosting the NK cell‐based immunotherapy, mainly through enhancing NK cell engagement with tumors, boosting NK cell activation or expansion, as well as redirecting NK cells to tumor cells, are reviewed. Lastly, the design and preparation of next‐generation nanomaterials that aim to further boost the NK cell‐based immunotherapy are briefly discussed.
Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity
Authors: Dantignana Valeria , Pérez‐Segura M. Carmen , Besalú‐Sala Pau , Delgado‐Pinar Estefanía , Martínez‐Camarena Álvaro , Serrano‐Plana Joan , Álvarez‐Núñez Andrea , Castillo Carmen E. , García‐España Enrique , Luis Josep M. , Basallote Manuel G. , Costas Miquel , Company Anna
Published: October 2022

Two oxoiron(IV) isomers (R2a and R2b) of general formula [FeIV(O)(RPyNMe3)(CH3CN)]2+ are obtained by reaction of their iron(II) precursor with NBu4IO4. The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between R2a and R2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that R2a reacts one order of magnitude faster than R2b, which is explained by a repulsive noncovalent interaction between the ligand and the substrate in R2b. Interestingly, the electronic properties of the R substituent in the ligand pyridine ring do not have a significant effect on reaction rates. Overall, the intrinsic structural aspects of each isomer define their relative HAT reactivity, overcoming changes in electronic properties of the ligand.
Native Amide‐Directed C(sp3)−H Amidation Enabled by Electron‐Deficient RhIII Catalyst and Electron‐Deficient 2‐Pyridone Ligand
Authors: Wakikawa Takumi , Sekine Daichi , Murata Yuta , Bunno Youka , Kojima Masahiro , Nagashima Yuki , Tanaka Ken , Yoshino Tatsuhiko , Matsunaga Shigeki
Published: October 2022

Trivalent group‐9 metal catalysts with a cyclopentadienyl‐type ligand (CpMIII; M=Co, Rh, Ir, Cp=cyclopentadienyl) have been widely used for directed C−H functionalizations, albeit that their application to challenging C(sp3)−H functionalizations suffers from the limitations of the available directing groups. In this report, we describe directed C(sp3)−H amidation reactions of simple amide substrates with a variety of substituents. The combination of an electron‐deficient CpERh catalyst (CpE=1,3‐bis(ethoxycarbonyl)‐substituted Cp) and an electron‐deficient 2‐pyridone ligand is essential for high reactivity.
A General Method to Edit Histone H3 Modifications on Chromatin Via Sortase‐Mediated Metathesis
Authors: Yang Qingyun , Gao Yingxiao , Liu Xia , Xiao Yihang , Wu Mingxuan
Published: October 2022

The post‐translational modifications (PTMs) on the tail of histone H3 control chromatin structure and influence epigenetics and gene expression. The current chemical methods including unnatural amino acid incorporation and protein splicing enable preparations of the histone with diverse PTMs in cellular contexts, but they are not applicable to edit native chromatin. The manipulation of histone‐modifying enzymes alter the endogenous histone PTMs but the lack of specificity of most histone‐modifying enzymes prevents precise control of specific H3 tail PTM patterns. Here we report a new method to edit the N‐tail of histone H3 via sortase mediated metathesis (SMM). The sortase can install desired PTM patterns into histone H3 on nucleosomes in vitro and in cellulo. This study expands the application scope of sortase from ligation to metathesis in live cells using cell‐penetrating peptides (CPPs). In addition, it offers a strategy to edit PTMs of cellular histone H3 with potential for the development of precise epigenome editing.
Spatiotemporally Controlled Formation and Rotation of Magnetic Nanochains In Vivo for Precise Mechanotherapy of Tumors
Authors: Fu Qinrui , Feng Hongjuan , Liu Luntao , Li Ziqiao , Li Jianjie , Hu Jing , Hu Chengzhi , Yan Xiaohui , Yang Huanghao , Song Jibin
Published: October 2022

Systemic cancer therapy is always accompanied with toxicity to normal tissue, which has prompted concerted efforts to develop precise treatment strategies. Herein, we firstly develop an approach that enables spatiotemporally controlled formation and rotation of magnetic nanochains in vivo, allowing for precise mechanotherapy of tumor. The nanochain comprised nanocomposites of pheophorbide‐A (PP) modified iron oxide nanoparticle (IONP) and lanthanide‐doped down‐conversion NP (DCNP). In a permanent magnetic field, the nanocomposites would be aligned to form nanochain. Next, MnO2 NPs were subsequently administered to accumulate in tumor as suppliers of Mn2+, which coordinates with PP to immobilize the nanochain. In a rotating magnetic field, the nanochain would rapidly rotate, leading to apoptosis/necrosis of tumor cell. The nanochain showed high T2‐MR and NIR‐II fluorescence imaging signals, which facilitated guided therapy. The strategy has great potential in practical applications.
Observation of an Alternate Charge‐Polarization State in a One‐Dimensional Pt−Pt−I Chain Compound with a Bulky Pendant Ligand
Authors: Moriyama Hayato , Otsubo Kazuya , Sugimoto Kunihisa , Kawaguchi Shogo , Kitagawa Hiroshi
Published: October 2022

A one‐dimensional (1D) halogen‐bridged dinuclear‐metal complex (MMX‐chain) exhibits various electronic states based on a mixed‐valence metal‐dimer system. This report deals with the synthesis and physical properties of a new MMX‐chain with a bulky pendant ligand, Pt2(mcc‐HexCS2)4I (mcc‐HexCS2=trans‐4‐(methoxycarbonyl)cyclohexanedithiocarboxylate). The steric hindrance caused by the bulky substituent induces a strain in its 1D chain, achieving at ambient condition the first pure alternate charge‐polarization (ACP) state (−Pt2+−Pt3+−I−−Pt3+−Pt2+−I−−), a kind of spin‐Peierls state, as confirmed by X‐ray diffraction and its conducting and magnetic properties. The strain effect is also manifested as a very large linear thermal expansion along the chain direction, which is quite different from conventional MMX‐chains without a bulky ligand. The design of low‐dimensional materials with ligand variations is expected to lead to the emergence of new electron–lattice coupled electronic states.
Effects of biofilm heterogeneity on the apparent mechanical properties obtained by shear rheometry
Authors: Li Mengfei , Nahum Yanina , Matouš Karel , Stoodley Paul , Nerenberg Robert
Published: October 2022

Rheometry is an experimental technique widely used to determine the mechanical properties of biofilms. However, it characterizes the bulk mechanical behavior of the whole biofilm. The effects of biofilm mechanical heterogeneity on rheometry measurements are not known. We used laboratory experiments and computer modeling to explore the effects of biofilm mechanical heterogeneity on the results obtained by rheometry. A synthetic biofilm with layered mechanical properties was studied, and a viscoelastic biofilm theory was employed using the Kelvin–Voigt model. Agar gels with different concentrations were used to prepare the layered, heterogeneous biofilm, which was characterized for mechanical properties in shear mode with a rheometer. Both experiments and simulations indicated that the biofilm properties from rheometry were strongly biased by the weakest portion of the biofilm. The simulation results using linearly stratified mechanical properties from a previous study also showed that the weaker portions of the biofilm dominated the mechanical properties in creep tests. We note that the model can be used as a predictive tool to explore the mechanical behavior of complex biofilm structures beyond those accessible to experiments. Since most biofilms display some degree of mechanical heterogeneity, our results suggest caution should be used in the interpretation of rheometry data. It does not necessarily provide the “average” mechanical properties of the entire biofilm if the mechanical properties are stratified.
Costimulatory molecule‐related lncRNA model as a potential prognostic biomarker in non‐small cell lung cancer
Authors: Yao Yuanshan , Yang Fuzhi , Chen Anna , Hua Qingwang , Gao Wen
Published: October 2022

Objective

Costimulatory molecules have been demonstrated to exert essential roles in multiple cancers. However, their role in lung cancer remains elusive. Here, we sought to identify costimulatory molecule‐related lncRNAs in non‐small cell lung cancer (NSCLC) and establish a prognostic signature to predict the prognosis of patients with NSCLC.

Methods

A total of 535 lung adenocarcinoma (LUAD) and 502 lung squamous cell carcinoma (LUSC) patients from the cancer genome atlas (TCGA) database were recruited. A novel costimulatory molecule‐based lncRNA prognostic model was constructed using the least absolute shrinkage and selection operator (LASSO) algorithm to predict the overall survival. The Homo_sapiens.GRCh38 data set was set as a reference file for probe annotation.

Results

A total of 593 costimulatory molecule‐related lncRNAs were extracted. After analysis, six costimulatory molecule‐related lncRNAs (AC084859.1, AC079949.2, HSPC324, LINC01150, LINC01150, and AC090617.5) were screened. A prognostic model based on the six lncRNAs was established using systematic bioinformatics analyses. The prognostic model had a prognostic value in NSCLC patients. Furthermore, a prognostic nomogram was established based on clinical parameters and a risk‐score model. Patients with different risk scores had considerably different tumor‐infiltrating immune cells, somatic mutational loading, clinical outcomes, signaling pathways, and immunotherapy efficacy. In addition, LINC01137 was associated with unfavorable disease outcomes and fueled tumor progression in NSCLC.

Conclusion

Taken together, our study demonstrated that a costimulatory molecule‐related lncRNA model could be a potential prognostic biomarker in NSCLC. Moreover, LINC01137 could facilitate the proliferation and invasion of lung cancer.
Diterpenoids from Strophioblachia glandulosa and Their NLRP3 Inflammasome Inhibitory Effects
Authors: Sakah Kaunda Joseph , Xu Yao‐Jun , Zhang Rui‐Han , Zhang Xing‐Jie , Li Xiao‐Li , Xiao Wei‐Lie
Published: October 2022

Our study on the roots and leaves of the never‐hitherto‐chemically studied S. glandulosa led to the isolation of five new diterpenes, referred to as stroglandulons A–E (1–5), alongside 18 known constituents (6–23). The structures of the new compounds were elucidated on the basis of their spectroscopic data, while the known ones were determined based on the comparison of their data with the literature values. Compounds 1–5 were evaluated for their inhibitory effects against NLRP3 inflammasome activation; compound 5 showed inhibition by an IC50 value of 6.12±0.03 μM.
Influence of Pore Size in Benzoin Condensation of Furfural Using Heterogenized Benzimidazole Organocatalysts
Authors: Miletto Ivana , Meazza Marta , Paul Geo , Cossi Maurizio , Gianotti Enrica , Marchese Leonardo , Rios Ramon , Pera‐Titus Marc , Raja Robert
Published: October 2022

A designed N‐heterocyclic carbene (NHC) catalyst was covalently anchored on a range of mesoporous and hierarchical supports, to study the influence of pore size in the benzoin condensation of furfural. The structural and spectroscopic characteristics of the anchored catalysts were investigated, also with the help of molecular dynamics simulations, in order to rationalize the degree of stability and recyclability of the heterogenized organocatalysts. Quantitative yields (99 %) and complete recyclability were maintained after several cycles, vindicating the design rationale.
Dual‐Readout of the Mechanical Response of a Bis‐acridinium [2]Rotaxane
Authors: Hu Johnny , Adrouche Sonia , Gauthier Etienne S. , Le Breton Nolwenn , Cecchini Marco , Gourlaouen Christophe , Choua Sylvie , Heitz Valérie , Jacquot de Rouville Henri‐Pierre
Published: October 2022

A [2]rotaxane built around a multi‐responsive bis‐acridinium macrocycle has been synthesized. Structural investigation has confirmed the interlocked nature of the molecule, and MD simulations illuminated its conformational dynamics with atomic resolution. Both halochromic and redox‐switching properties were explored to shed light on the mechanical response and electronic changes that occur in the bis‐acridinium [2]rotaxane. The topology of the rotaxane led to different mechanical behaviors upon addition of hydroxide ions or reduction that were easily detected by UV/Vis spectroscopy and electrochemistry.
Stereodivergent Total Syntheses of (+)‐Mycaperoxides C, D, G Methyl Ester and (−)‐Mycaperoxide B**
Authors: Kerim Mansour D. , Evanno Laurent , Ferrié Laurent
Published: October 2022

Mycaperoxides are natural endoperoxides isolated from different Mycale genus sponges, showing significant antiviral or antibacterial activities. We report herein the first total syntheses of representative congeners of this family from sclareol using a stereodivergent approach. Thus, an innovative oxidative ring expansion of cyclobutanol was used to bring the 1,2‐dioxane subunit, and a Mukaiyama aldol reaction on peroxycarbenium species was utilized to install the propionic acid subunit. During the study toward (+)‐mycaperoxide D methyl ester (2), the isolation of the eight possible diastereomers under their ethyl thioester form allowed to build a pertinent database for further NMR assignment studies. Thus, we completed the total syntheses of (+)‐mycaperoxides D, C, G methyl ester, and (−)‐mycaperoxide B in 11 to 15 steps, confirming their original assignment.
Iron‐Catalysed Carbene Transfer to Isocyanides as a Platform for Heterocycle Synthesis
Authors: Roose Thomas R. , Preschel H. Daniel , Mayo Tejedor Helena , Roozee Jasper C. , Hamlin Trevor A. , Maes Bert U. W. , Ruijter Eelco , Orru Romano V. A.
Published: October 2022

An iron‐catalysed carbene transfer reaction of diazo compounds to isocyanides has been developed. The resulting ketenimines are trapped in situ with various bisnucleophiles to access a range of densely functionalized heterocycles (pyrimidinones, dihydropyrazolones, 1H‐tetrazoles) in a one‐pot process. The electron‐rich Hieber anion ([Fe(CO)3NO]−) facilitates efficient catalytic carbene transfer from acceptor‐type α‐diazo carbonyl compounds to isocyanides, providing a cost‐efficient and benign alternative to similar noble metal‐catalysed processes. Based on DFT calculations a plausible reaction mechanism for activation of the α‐diazo carbonyl carbene precursor and ketenimine formation is provided.
Accomplishing Scalability by Using Plate‐Based Freeze and Thaw Technologies
Authors: Jenewein Roland , Breitrainer Michael
Published: October 2022

Controlling the freezing behavior of bulk drug substance opens doors to process reproducibility and consistent quality of the final drug product by maintaining uniform conditions for the biopharmaceuticals during freezing, and consequently for frozen storage and shipment. This simplifies the commercial bulk production, particularly when manufacturing different drug substances at different sensitivities and temperature set points and enables scalability. The leverage of the ice front growth speed had a significant impact on controllability and, as a result, on the protein quality.
Automation of Integrated Perfusion Control Simplifying Process Intensification of Mammalian Biomanufacturing in Single‐Use Bioreactors
Authors: Schulze Markus , Kues Dominic , Gao Wei , Houser Matthew , Scheibenbogen Karl‐Heinz , Husemann Bernward , Husemann Ute , Greller Gerhard
Published: October 2022

Production of biopharmaceuticals needs to become faster, more flexible, and efficient. Perfusion processes allow to operate cell cultivations at higher cell concentrations, shorten their process time and increase their productivity. Still, either customized software solutions or third‐party stand‐alone control devices are often used for perfusion control. Its integration into a bioreactor automation platform will simplify the implementation and application of perfusion processes in the future. In this study, the automation of an integrated perfusion control strategy for a scalable single‐use bioreactor family is demonstrated. The control strategy is illustrated by means of a CHO cell N–1 perfusion process in a 50‐L bioreactor. Accurate control allowed to achieve 80 · 106 c mL−1 within five days. Furthermore, also DO and pH setpoints were precisely controlled throughout the N–1 perfusion process. Finally, the advantage of this process strategy is exemplified by comparing fed‐batch processes inoculated from N–1 perfusion vs. N–1 batch processes.
A Triethyleneglycol C60 Mono‐adduct Derivative for Efficient Electron Transport in Inverted Perovskite Solar Cells†
Authors: Fakharuddin Azhar , Armadorou Konstantina‐Kalliopi , Zorba Leandros P. , Tountas Marinos , Seewald Tobias , Soultati Anastasia , Tsipas Polychronis , Schütz Emilia R. , Tzoganakis Nikolaos , Panagiotakis Stylianos , Yannakopoulou Konstantina , Dimoulas Athanasios , Psycharis Vassilis , Kymakis Emmanuel , Yusoff Abd Rashid bin Mohd , Aidinis Konstantinos , Schmidt‐Mende Lukas , Vougioukalakis Georgios C. , Nazeeruddin Mohammad Khaja , Vasilopoulou Maria
Published: October 2022

Comprehensive Summary

Inverted perovskite solar cells (PSCs) have attracted increasing attention in recent years owing to their low‐temperature fabrication proces s. However, they suffer from a limited number of electron transport materials available with [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) to be the most widely studied based on its appropriate energy levels and high electron mobility. The low relative permittivity and aggregation tendency upon illumination of PCBM, however, compromises the solar cell efficiency whereas its modest hydrophobicity negatively impacts on the device stability. Alternative electron transport materials with desired properties and appropriate degree of hydrophobicity are thus desirable for further developments in inverted PSCs. Herein, we synthesize a triethyleneglycol C60 mono‐adduct derivative (termed as EPF03) and test it as a novel electron transport material to replace PCBM in inverted PSCs based on a quadruple cation (RbCsMAFA) perovskite. We also compare this derivative with two novel fullerenes decorated with two (EPF01) or one dodecyl (EPF02) long side chains. The latter two fail to perform efficiently in inverted PSCs whereas the former enabled a power conversion efficiency of 18.43%, which represents a 9% improvement compared to the reference device using PCBM (17.21%). The enhanced performance mainly stems from improved electron extraction and reduced recombination enabled by the insertion of the large relative permittivity amongst other properties of EPF03. Furthermore, our results indicate that triethylene glycol side chains can also passivate perovskite trap states, suppress ion migration and enhance photostability and long‐term stability of EPF03 based perovskite solar cells.
Sparse estimation of historical functional linear models with a nested group bridge approach
Authors: Xun Xiaolei , Guan Tianyu , Cao Jiguo
Published: October 2022

The conventional historical functional linear model relates the current value of the functional response at time to all past values of the functional covariate up to time . Motivated by situations where it is more reasonable to assume that only recent, instead of all, past values of the functional covariate have an impact on the functional response, in this work we investigate the historical functional linear model with an unknown forward time lag into the history. In addition to estimating the bivariate regression coefficient function, we also aim to identify the historical time lag from the data, which is important in many applications. To this end, we propose an estimation procedure that uses the finite element method to conform naturally to the trapezoidal domain of the bivariate coefficient function. We use a nested group bridge penalty to facilitate simultaneous estimation of the bivariate coefficient function and the historical lag, and show that our proposed estimators are consistent. We demonstrate this method of estimation in a real data example investigating the effect of muscle activation recorded via the noninvasive electromyography (EMG) method on lip acceleration during speech production. In addition, we examine the finite sample performance of our proposed method in comparison with the conventional approach to estimation via simulation studies.
Potential risk factors for acute grief during the COVID‐19 pandemic: The mediating role of avoidance processes
Authors: Zou Xinyan , Xu Xin , Tang Renzhihui , Jiao Keyuan , Qian Wenli , Shen Xinlan , Wang Jianping
Published: October 2022

Bereavement during the COVID‐19 pandemic may have some unique characteristics that become potential risk factors (e.g., absence of grief rituals, no opportunity to say goodbye to the deceased and loneliness caused by social distancing) for acute grief. Avoidance processes could be significant mediators in the context of the pandemic. The current study aimed to investigate whether and how these COVID‐19‐related risk factors were related to acute grief severity. Bereaved adults (n = 319) who lost significant others during the COVID‐19 pandemic completed a self‐report questionnaire package measuring COVID‐19‐related factors, grief severity and depressive and anxious avoidance. Regression analyses suggested that among the three potential risk factors (loneliness, grief rituals and opportunity to say goodbye), loneliness was significantly associated with acute grief after controlling for basic demographic and loss‐related information. Structural equation models suggested that depressive avoidance and anxious avoidance partially mediated the associations of loneliness with acute grief severity. The findings indicate that dealing with loss during the COVID‐19 pandemic warrants further exploration concerning how potential environmental risk factors may impede adaptation to loss. Depressive and anxious avoidance processes may play important roles in grief interventions for isolated and lonely bereaved people.
Speech and language characteristics differentiate Alzheimer's disease and dementia with Lewy bodies
Authors: Yamada Yasunori , Shinkawa Kaoru , Nemoto Miyuki , Ota Miho , Nemoto Kiyotaka , Arai Tetsuaki
Published: October 2022

Introduction

Early differential diagnosis of Alzheimer's disease (AD) and dementia with Lewy bodies (DLB) is important, but it remains challenging. Different profiles of speech and language impairments between AD and DLB have been suggested, but direct comparisons have not been investigated.

Methods

We collected speech responses from 121 older adults comprising AD, DLB, and cognitively normal (CN) groups and investigated their acoustic, prosodic, and linguistic features.

Results

The AD group showed larger differences from the CN group than the DLB group in linguistic features, while the DLB group showed larger differences in prosodic and acoustic features. Machine‐learning classifiers using these speech features achieved 87.0% accuracy for AD versus CN, 93.2% for DLB versus CN, and 87.4% for AD versus DLB.

Discussion

Our findings indicate the discriminative differences in speech features in AD and DLB and the feasibility of using these features in combination as a screening tool for identifying/differentiating AD and DLB.
Glucose variability: A physiological correlate of eating disorder behaviors among individuals with binge‐spectrum eating disorders
Authors: Presseller Emily K. , Patarinski Anna Gabrielle G. , Zhang Fengqing , Page Kathleen A. , Srivastava Paakhi , Manasse Stephanie M. , Juarascio Adrienne S.
Published: October 2022

Objectives

Elevated glucose variability may be one mechanism that increases risk for significant psychological and physiological health conditions among individuals with binge‐spectrum eating disorders (B‐EDs), given the impact of eating disorder (ED) behaviors on blood glucose levels. This study aimed to characterize glucose variability among individuals with B‐EDs compared with age‐matched, sex‐matched, and body mass index‐matched controls, and investigate the association between frequency of ED behaviors and glucose variability.

Methods

Participants were 52 individuals with B‐EDs and 22 controls who wore continuous glucose monitors to measure blood glucose levels and completed ecological momentary assessment surveys to measure ED behaviors for 1 week. Independent samples t‐tests compared individuals with B‐EDs and controls and multiple linear regression models examined the association between ED behaviors and glucose variability.

Results

Individuals with B‐EDs demonstrated numerically higher glucose variability than controls (t = 1.42, p = .08, d = 0.43), although this difference was not statistically significant. When controlling for covariates, frequency of ED behaviors was significantly, positively associated with glucose variability (t = 3.17, p = .003) with medium effect size (f2 = 0.25). Post hoc analyses indicated that binge eating frequency was significantly associated with glucose variability, while episodes of 5+ hours without eating were not.

Discussion

Glucose variability among individuals with B‐EDs appears to be positively associated with engagement in ED behaviors, particularly binge eating. Glucose variability may be an important mechanism by which adverse health outcomes occur at elevated rates in B‐EDs and warrants future study.

Public Significance

This study suggests that some individuals with binge ED and bulimia nervosa may experience elevated glucose variability, a physiological symptom that is linked to a number of adverse health consequences. The degree of elevation in glucose variability is positive associated with frequency of eating disorder behaviors, especially binge eating.
Deoxygenative Chlorination of Aldehydes and Alcohols with Dichloromethyl Methyl Ether and TiCl4
Authors: Polat Emrah , Cakici Murat
Published: October 2022

Here, we report highly efficient deoxygenative chlorination of aldehydes and alcohols with a dichloromethyl methyl ether and TiCl4 system. The method converts various aldehydes and alcohols into the desired geminal dichlorides or chlorides with good to excellent yields (up to 99 %). Combined with a subsequent Rieche formylation step using the same reagent system, this method provides an efficient approach for synthesis of aromatic dialdehydes. This strategy involves deoxy‐chlorination of the aryl aldehydes followed by a second formylation of more activated benzal chloride derivatives. Dialdehydes can be easily obtained by hydrolyzing the corresponding of dichloromethyl derivative.
Energy and water: COVID‐19 impacts and implications for interconnected sustainable development goals
Authors: Bhattacharya Riya , Bose Debajyoti
Published: October 2022

The COVID‐19 pandemic presented a chance to investigate the effects of system‐wide emergencies on major global commodities such as water and energy. In terms of environmental policies and attaining supply security, these developmental goals are interrelated. Despite pandemic disruptions, there is a compelling need for a systematization in these areas for the transition to clean water access and sustainable energy. This article presents a comprehensive assessment of the effects of COVID‐19 on these two sustainable development goals. Further, an integrated aspect of water and energy access for sustainable development is evaluated with insights on the effects of COVID‐19 on the water‐energy nexus. Additionally, technological evolution for building better water and energy supply systems is presented. An insight into developing robust healthcare systems and how the water and energy SDGs affect population dynamics is also speculated, which indicates varied short‐term adaption experiences, and highlights the need for a re‐evaluation of the water‐energy nexus. The integrated solutions contributing to stability of the water supply chain, energy storage, and policy making during and after an outbreak are critical to achieving developmental goals.
Evolutionary seismic design optimization of mega‐brace damper architectures in three‐dimensional structures
Authors: Apostolakis Georgios , Wang Tiancheng , Blanco Hector
Published: October 2022

Novel seismic protection systems are widely used to improve building performance or collapse prevention under extreme events. However, a systematic approach for the distribution of dampers in structures expected to operate inelastically under extreme seismic loading does not exist in modern seismic codes. Furthermore, optimal designs are achieved typically performing only forward analysis with no direction on how device topologies and properties distribution affect the response and the plastic action distribution throughout structures for different types of passive devices. To address the above, this study utilizes an evolutionary framework for optimization of the topology and properties of passive dampers in three‐dimensional buildings subject to seismic loading. The framework incorporates a self‐organizing evolutionary algorithm, a novel concept of mega‐brace damper architecture scheme, and an active ground motion subset scheme to efficiently find optimal designs that satisfy predefined performance targets. Three‐dimensional buildings considered include eight‐story irregular, eight‐story regular, and 14‐story regular structures, while passive devices included yielding, friction, and viscous dampers. The seismic environment consisted of twenty‐five synthetic ground motions with 5% of probability of exceedance in 50 years. The study included design examples with realistic three‐dimensional buildings, and the proposed framework yielded optimal designs that exhibited uniform ductility demand along the height when compared to the base buildings. Novel three‐dimensional multiscale mega‐brace architectures not seen in practice were identified, while their corresponding plastic action distribution throughout the buildings was assessed for each case.
Palestinian feminism: Analytics, praxes and decolonial futures
Authors: Ihmoud Sarah
Published: October 2022

This article theorizes Palestinian feminism as an analytical lens and a political project. Grounded in histories and ongoing organizing for anticolonial liberation, it outlines contemporary challenges and possibilities for Palestinian feminist organizing in the homeland and the shataat. Further, it centers Palestine as a space for enacting feminist praxis more broadly, and calls on feminist scholars and activists to join the struggle for Palestinian liberation.
A two‐phase flow extended finite element technology modeling CO2 in fractured porous media
Authors: Luo Zhifeng , Xie Yaozeng , Zhao Liqiang , Cheng Long , Wen Guohua
Published: October 2022

Carbon dioxide (CO2) geological sequestration technology is an attractive means of reducing greenhouse gas emissions. This work aims to seek the transport mechanism of CO2 in fractured porous media. A two‐phase flow extended finite element model is developed in this paper. The two‐phase flow in the fracture and porous matrix are all considered in the model development. We present numerical simulations under 2D linear flow conditions with specific and sensitivity analysis about fracture properties, capillary pressure, relative permeability, reservoir heterogeneity, and properties. It is found that fracture will dominate the CO2 transport when the intersection angle of fracture orientation and injection direction is less than 90°, and CO2 flows into deeper regions along the fracture. It is significant to find a suitable capillary pressure and relative permeability model which matches the microscopic pore structure when simulating CO2 geological sequestration in fractured media. Using the Brooks–Corey equation for capillary pressure and relative permeability, the CO2 transport efficiency would increase by around 16% compared to the Van Gneuchten equation. Besides, the CO2 phase and properties evolution during CO2 geological sequestration has a great influence on CO2 transport efficiency., CO2 transport efficiency is reduced by around 18% due to an increase in CO2 density and viscosity when considering CO2 properties evolution. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.