bluuebunny/crossref_metadata_2025 huggingface dataset:
Enantioselective Synthesis of Acyclic Stereotriads Featuring Fluorinated Tetrasubstituted Stereocenters
Authors: Shao Na , Liu Xueyang , Monnier Valérie , Charles Laurence , Rodriguez Jean , Bressy Cyril , Quintard Adrien
Published: November 2021

Elaboration of enantioenriched complex acyclic stereotriads represents a challenge for modern synthesis even more when fluorinated tetrasubstituted stereocenters are targeted. We have been able to develop a simple strategy in a sequence of two unprecedented steps combining a diastereoselective aldol‐Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution. The aldol‐Tishchenko reaction directly generates a large panel of acyclic 1,3‐diols possessing a fluorinated tetrasubstituted stereocenter by condensation of fluorinated ketones with aldehydes under very mild basic conditions. The anti 1,3‐diols featuring three contiguous stereogenic centers are generated with excellent diastereocontrol (typically >99 : 1 dr). Depending upon the precursors both diastereomers of stereotriads are accessible through this flexible reaction. Furthermore, from the obtained racemic scaffolds, development of an organocatalyzed kinetic resolution enabled to generate the desired enantioenriched stereotriads with excellent selectivity (typically er >95 : 5).
Understanding the Preparation and Reactivity of Mo/ZSM‐5 Methane Dehydroaromatization Catalysts
Authors: Liu Yujie , Zhang Hao , Wijpkema Alexandra S. G. , Coumans Ferdy J. A. G. , Meng Lingqian , Uslamin Evgeny A. , Longo Alessandro , Hensen Emiel J. M. , Kosinov Nikolay
Published: November 2021

Methane dehydroaromatization is a promising reaction for the direct conversion of methane to liquid hydrocarbons. The active sites and the mechanism of this reaction remain controversial. This work is focused on the operando X‐ray absorption near edge structure spectroscopy analysis of conventional Mo/ZSM‐5 catalysts during their whole lifetime. Complemented by other characterization techniques, we derived spectroscopic descriptors of molybdenum precursor decomposition and its exchange with zeolite Brønsted acid sites. We found that the reduction of Mo‐species proceeds in two steps and the active sites are of similar nature, regardless of the Mo content. Furthermore, the ZSM‐5 unit cell contracts at the beginning of the reaction, which coincides with benzene formation and it is likely related to the formation of hydrocarbon pool intermediates. Finally, although reductive regeneration of used catalysts via methanation is less effective as compared to combustion of coke, it does not affect the structure of the catalysts.
Accessing Cationic α‐Silylated and α‐Germylated Phosphorus Ylides
Authors: Krämer Felix , Radius Michael , Hinz Alexander , Dilanas Melina E. A. , Breher Frank
Published: November 2021

The synthesis and full characterization of α‐silylated (α‐SiCPs; 1–7) and α‐germylated (α‐GeCPs; 11–13) phosphorus ylides bearing one chloride substituent R3PC(R1)E(Cl)R22 (R=Ph; R1=Me, Et, Ph; R2=Me, Et, iPr, Mes; E=Si, Ge) is presented. The molecular structures were determined by X‐ray diffraction studies. The title compounds were applied in halide abstraction studies in order to access cationic species. The reaction of Ph3PC(Me)Si(Cl)Me2 (1) with Na[B(C6F5)4] furnished the dimeric phosphonium‐like dication [Ph3PC(Me)SiMe2]2[B(C6F5)4]2 (8). The highly reactive, mesityl‐ or iPr‐substituted cationic species [Ph3PC(Me)SiMes2][B(C6F5)4] (9) and [Ph3PC(Et)SiiPr2][B(C6F5)4] (10) could be characterized by NMR spectroscopy. Carrying out the halide abstraction reaction in the sterically demanding ether iPr2O afforded the protonated α‐SiCP [Ph3PCH(Et)Si(Cl)iPr2][B(C6F5)4] (6 dec) by sodium‐mediated basic ether decomposition, whereas successfully synthesized [Ph3PC(Et)SiiPr2][B(C6F5)4] (10) readily cleaves the F−C bond in fluorobenzene. Thus, the ambiphilic character of α‐SiCPs is clearly demonstrated. The less reactive germanium analogue [Ph3PC(Me)GeMes2][B{3,5‐(CF3)2C6H3}4] (14) was obtained by treating 11 with Na[B{3,5‐(CF3)2C6H3}4] and fully characterized including by X‐ray diffraction analysis. Structural parameters indicate a strong CYlide−Ge interaction with high double bond character, and consequently the C−E (E=Si, Ge) bonds in 9, 10 and 14 were analyzed with NBO and AIM methods.
Domino Dehydrative π‐Extension: A Facile Path to Extended Perylenes and Terrylenes
Authors: Feofanov Mikhail , Akhmetov Vladimir , Amsharov Konstantin
Published: November 2021

Invited for the cover of this issue is the group of Konstantin Amsharov at Martin Luther University Halle–Wittenberg and Friedrich Alexander University Erlangen–Nürnberg. The image depicts tribenzoterrylene synthesized via the domino‐DPEX reaction. Read the full text of the article at 10.1002/chem.202103098.
Visible‐Light‐Enabled Carboxylation of Benzyl Alcohol Derivatives with CO2 Using a Palladium/Iridium Dual Catalyst
Authors: Jin Yushu , Toriumi Naoyuki , Iwasawa Nobuharu
Published: November 2021

A highly efficient carboxylation of benzyl alcohol derivatives with CO2 using a palladium/iridium dual catalyst under visible‐light irradiation was developed. A wide range of benzyl alcohol derivatives could be employed to provide benzylic carboxylic acids in moderate to high yields. Mechanistic studies indicated that the oxidative addition of benzyl alcohol derivatives was possibly the rate‐determining‐step. It was also found that a switchable site‐selective carboxylation between benzylic C−O and aryl C−Cl moieties could be achieved simply by changing the palladium catalyst.
Mechanochemical Preparation of Protein : hydantoin Hybrids and Their Release Properties
Authors: Yuan Yusheng , Wang Lei , Porcheddu Andrea , Colacino Evelina , Solin Niclas
Published: November 2021

Mechanochemistry is a versatile methodology that can be employed both for covalent bond formation in organic synthesis as well as a mediator to allow preparation novel colloidal dispersions for drug delivery. Herein, ball‐milling was employed for the solid‐state preparation of fluorescent hydrophobic hydantoins, followed by the unprecedented mechanochemically‐mediated complexation of hydrophobic hydantoins within hydrophilic protein β‐lactoglobulin (BLG) and BLG nanofibrils (BLGNFs). These hydantoin:protein materials were in turn incorporated into hydrogels. The effect of incorporation of hydantoins into proteins, as well as the effect of protein structure, on the release properties were then investigated. The conversion of BLG to BLGNFs led to a more sustained release demonstrating that heat treatment of BLG into BLGNFs could be employed to modify release properties. To the best of our knowledge, this is the first example where protein : hydantoin complexes were prepared by mechanochemical methodology and mechanochemistry was combined with self‐assembly in order to prepare protein nanomaterials for drug‐delivery applications. In addition, the use of the developed protein materials is not limited to delivery of drugs but can for example be employed as components of smart food (delivery of nutrients) or release systems of pesticides.
The application of multidisciplinary therapy strategy of precision medicine in tumour diagnosis and treatment
Authors: Qian Mengjia , Chen Hao , Wu Duojiao , Qiao Tiankui , Shen Hui , Cheng Yunfeng
Published: November 2021

The purpose of the establishment of multidisciplinary therapy (MDT) strategy of precision medicine is to provide professional gene interpretation and consultation, combined with the expertise of clinicians, to develop personalized treatment strategies for patients. In this article, we report four typical cases to demonstrate the process and working mode of MDT strategy of precision medicine, and what it could bring to clinicians or patients is also discussed.
Cytokine storm after heart transplantation in COVID‐19‐related haemophagocytic lymphohistiocytosis (HLH)
Authors: Mahdavi Mohammad , Hejri Golnar Mortaz , Pouraliakbar Hamidreza , Shahzadi Hossein , Hesami Mahshid , Houshmand Golnaz
Published: November 2021

While severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) infection primarily causes inflammation in the respiratory system, there is growing evidence of extrapulmonary tissue damage mediated by the host innate immune system in children and adults. A cytokine storm can manifest as a viral‐induced haemophagocytic lymphohistiocytosis (HLH). Here, we present a previously healthy 8‐year‐old boy with newly diagnosed cardiac injury and COVID‐19‐related HLH syndrome with haemophagocytosis in bone marrow biopsy. After remission of inflammation, the patient underwent a heart transplant due to persistent cardiac failure. The histology of the explanted heart showed only a focal subtle subendocardial inflammation. Three days after transplant, he developed progressive acute respiratory distress syndrome (ARDS) with the rise of inflammatory markers. He unfortunately died after 20 days because of disseminated intravascular coagulation (DIC). For the first time, we described a child with COVID‐19‐related HLH and severe cardiac failure, which had a poor prognosis despite a heart transplant.
Quantitative Studies on the Structure of Zirconium Fluoride Anions in Molten LiF and FLiBe
Authors: Liu Xiyan , Hu Jingwen , Wang Chenyang
Published: November 2021

The quantitative distribution of different zirconium fluoride anions in molten LiF and FLiBe mixtures has been investigated by Raman and theoretical calculations. In molten LiF, zirconium fluorides are present in the forms of ZrF62− and ZrF73−. After correction, the Raman scattering cross sections corresponding to the symmetric stretching vibrational bands were obtained. The ZrF73− anion was a dominant species whatever the concentration of ZrF4 between 5 and 30 mol % in LiF melt, even though the content of which presents a decreasing trend from 92.3 to 73.2 mol % with the increase of ZrF4. Similar specification was identified in FLiBe‐ZrF4, and ZrF62−/ZrF73− anions were found in equilibrium with free F− ions and beryllium fluoride anions. Detailed deconvolution and calculation were performed on the Raman spectrum measured in the FLiBe melt containing 10 mol % ZrF4 giving a quantitative content of ZrF73− 78.1 mol % and ZrF62− 21.9 mol %.
Helical Chirality of Ferrocene Moieties in Cyclic Ferrocene‐Peptide Conjugates
Authors: Moriuchi Toshiyuki
Published: November 2021

Ferrocene has been utilized as an organometallic scaffold for more than 25 years, serving as a central reverse‐turn unit with the inter‐ring spacing of about 3.3 Å. A variety of ferrocene‐peptide conjugates have been designed to construct protein secondary structures and demonstrate the chirality organization via hydrogen bonding. In general, the helical chirality of ferrocene moieties in acyclic ferrocene‐peptide conjugates is induced by the absolute configuration of the α‐carbon atom of an amino acid adjacent to the ferrocene unit. Cyclization regulations restrict conformational flexibility of the peptide chains, inducing inversion of the helical chirality based on the reordering of the hydrogen bonding interactions. In this Minireview article, the helical chirality of ferrocene moieties in cyclic ferrocene‐peptide conjugates is focused on. Controlled helical chirality of ferrocene moieties in a series of ferrocene‐peptide conjugates by adjusting conformational flexibility of the peptide chains through cyclization regulations is introduced.
Catalytic Hydrogenation of Substituted Quinolines on Co–Graphene Composites
Authors: Asaula Vitalii M. , Buryanov Volodymyr V. , Solod Bohdan Y. , Tryus Daryna M. , Pariiska Olena O. , Kotenko Igor E. , Volovenko Yulian M. , Volochnyuk Dmitriy M. , Ryabukhin Sergey V. , Kolotilov Sergey V.
Published: November 2021

A set of 20 composites was prepared by pyrolysis of Co2+ complexes with 1,10‐phenanthroline, melamine and 1,2‐diaminobenzene. These composites were tested as the catalysts for the hydrogenation of quinolines. As shown by powder X‐ray diffraction and TEM, the composited contained Co particles of several dozen nm sizes. The composition (elements content), Raman spectra X‐ray photoelectron spectra parameters of the composites were analyzed. It was found that there was no distinct factor that controlled the yield of 1,2,3,4‐tetrahydroquinolines in the investigated process. The yields of the respective products were in the range 90–100 %. The three most active composites were selected for scale‐up and hydrogenation of a series of substituted quinolines. Up to 97 % yield of 1,2,3,4‐tetrahydroquinoline was obtained on a 50 g scale. Five representative substituted quinolines were synthesized on a 10–20 grams scale using the Co‐containing composites as the catalysts.
Noninvasively Collected Fecal Samples as Indicators of Multiple Pesticide Exposure in Wild Birds
Authors: Esther Alexandra , Schenke Detlef , Heim Wieland
Published: November 2021

Pesticide use poses a potential hazard to wild birds that use agricultural farmland as their foraging habitat. Whereas most current pesticide studies have found residues in liver samples and single active substances, noninvasive sampling methods and data on a wide variety of agrochemicals are needed to determine pesticide exposure of living wild birds for postregistration monitoring. We collected feces during autumn migration of Eurasian skylarks (Alauda arvensis), a species that commonly forages in winter cereal crops. Birds were kept in paper bags until we measured their body condition, individually marked and released them. We analyzed the feces dropped in paper bags for the presence of 80 pesticides including rodenticides and degradation products. Nine active substances from fungicides and herbicides commonly used in grain and maize fields were detected individually, or in combination, in 25% of the samples. We found no significant differences in body condition between exposed and unexposed birds, but Eurasian skylarks without pesticide residues had a better body condtion score on average than birds with pesticide residues. Pesticide determination in noninvasively collected fecal samples allows a refined risk analysis, which takes pesticides used in the habitats of birds into account. It allows the search for the sources of pesticide contamination, but also enables research into potential deleterious effects on the fitness of farmland birds. Environ Toxicol Chem 2022;41:201–207. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
L‐ornithine L‐aspartate in acute treatment of severe hepatic encephalopathy: A double‐blind randomized controlled trial
Authors: Jain Arpan , Sharma Barjesh Chander , Mahajan Bhawna , Srivastava Siddharth , Kumar Ajay , Sachdeva Sanjeev , Sonika Ujjwal , Dalal Ashok
Published: November 2021

Background and Aims

Data on the use of intravenous L‐ornithine L‐aspartate (LOLA) in the treatment of overt HE (OHE) is limited. We evaluated the role of intravenous LOLA in patients of cirrhosis with OHE grade III–IV.

Approach and Results

In a double‐blind randomized placebo‐controlled trial, 140 patients were randomized to a combination of LOLA, lactulose, and rifaximin (n = 70) or placebo, lactulose, and rifaximin (n = 70). LOLA was given as continuous intravenous infusion at a dose of 30 g over 24 h for 5 days. Ammonia levels, TNF‐α, ILs, and endotoxins were measured on days 0 and 5. The primary outcome was the improvement in the grade of HE at day 5. Higher rates of improvement in grade of HE (92.5% vs. 66%, p < 0.001), lower time to recovery (2.70 ± 0.46 vs. 3.00 ± 0.87 days, p = 0.03), and lower 28‐day mortality (16.4% vs. 41.8%, p = 0.001) were seen in the LOLA group as compared with placebo. Levels of inflammatory markers were reduced in both groups. Significantly higher reductions in levels of blood ammonia, IL‐6, and TNF‐α were seen in the LOLA group.

Conclusions

Combination of LOLA with lactulose and rifaximin was more effective than only lactulose and rifaximin in improving grades of HE, recovery time from encephalopathy, with lower 28‐day mortality.
The sustainable agriculture imperative: A perspective on the need for an agrosystem approach to meet the United Nations Sustainable Development Goals by 2030
Authors: Shahmohamadloo René S. , Febria Catherine M. , Fraser Evan D. G. , Sibley Paul K.
Published: November 2021

The development of modern, industrial agriculture and its high input–high output carbon energy model is rendering agricultural landscapes less resilient. The expected continued increase in the frequency and intensity of extreme weather events, in conjunction with declining soil health and biodiversity losses, could make food more expensive to produce. The United Nations has called for global action by establishing 17 sustainable development goals (SDGs), four of which are linked to food production and security: declining biodiversity (SDG 15), loss of ecosystem services and agroecosystem stability caused by increasing stress from food production intensification and climate change (SDG 13), declining soil health caused by agricultural practices (SDGs 2 and 6), and dependence on synthetic fertilizers and pesticides to maintain high productivity (SDG 2). To achieve these SDGs, the agriculture sector must take a leading role in reversing the many negative environmental trends apparent in today's agricultural landscapes to ensure that they will adapt and be resilient to climate change in 2030 and beyond. This will demand fundamental changes in how we practice agriculture from an environmental standpoint. Here, we present a perspective focused on the implementation of an agrosystem approach, which we define to promote regenerative agriculture, an integrative approach that provides greater resilience to a changing climate, reverses biodiversity loss, and improves soil health; honors Indigenous ways of knowing and a holistic approach to living off and learning from the land; and supports the establishment of emerging circular economies and community well-being. Integr Environ Assess Manag 2022;18:1199–1205. © 2021 SETAC

KEY POINTS

The agrosystem approach promotes regenerative agriculture, an integrative approach that can provide greater resilience to a changing climate, reverse biodiversity loss, and improve soil health. The agrosystem approach honors Indigenous ways of knowing and a holistic approach to living off and learning from the land The agrosystem approach supports the establishment of emerging circular economies and community well-being
Effects of plant biostimulants on seedling root and shoot growth of three cool‐season turfgrass species in a controlled environment
Authors: Acuña Alejandra , Gardner David , Villalobos Luis , Danneberger Karl
Published: November 2021

A plant biostimulant is a natural substance or microorganism applied to plants or soil to enhance growth and stress tolerance. The objective of this study was to measure the effect of six commercial plant biostimulants on root and shoot production in seedlings of three cool‐season turf species grown in a controlled environment. Lolium perenne L., Agrostis palustris Huds., and Schedonorus arundinaceus Schreb. were seeded into tobacco float trays and, after germination, were installed in a hydroponic system receiving a half‐dose Hoagland solution. Fifteen days after seeding, seedlings were treated with six different plant biostimulants applied within each float tray and then grown in a greenhouse for 25 d, following a split‐plot design. Photosynthetically active radiation, air temperature, and humidity were monitored for the duration of the study. The experiment was conducted twice. Fresh weight, dry weight, and total nonstructural carbohydrates were measured. The study showed that humic substances and complex organic materials had a positive effect on turfgrass performance, and there are species differences in the responses of turfgrass.
A phenomenological study of perseverance and resilience through the migration journey
Authors: Cigrand Dawnette L. , Fawcett Mary , Miyakuni Rieko , Arredondo Patricia , Onderak Gail
Published: November 2021

Researchers in this study used a phenomenological approach (Moustakas, 1994) to conduct and analyze interviews of 15 Latinx and Asian immigrants and refugees who shared their pre‐migration, migration, and post‐migration experiences. The participants were also asked to describe their perceived counseling needs at each stage of their journey. Four themes were identified: dire decisions, resilience and perseverance, trauma and loss, and human rights violations. Implications include the need for counselors to understand the journey experiences of immigrants and refugees, recognize their resilience and perseverance, and engage in advocacy‐based counseling approaches that are essential when supporting clients who identify as immigrants or refugees during their resettlement and post‐immigration period.
Understanding the impact of missense mutations on the structure and function of the EDA gene in X‐linked hypohidrotic ectodermal dysplasia: A bioinformatics approach
Authors: Ranjan Prashant , Das Parimal
Published: November 2021

X‐linked hypohidrotic dysplasia (XLHED), caused by mutations in the EDA gene, is a rare genetic disease that affects the development and function of the teeth, hair, nails, and sweat glands. The structural and functional consequences of caused by an ectodysplasin‐A (EDA) mutations on protein phenotype, stability, and posttranslational modifications (PTMs) have not been well investigated. The present investigation involves five missense mutations that cause XLHED (L56P, R155C, P220L, V251M, and V322A) in different domains of EDA (TM, furin, collagen, and tumor necrosis factor [TNF]) from previously published papers. The deleterious nature of EDA mutant variants was identified using several computational algorithm tools. The point mutations induce major drifts in the structural flexibility of EDA mutant variants and have a negative impact on their stability, according to the 3D protein modeling tool assay. Using the molecular docking technique, EDA/EDA variants were docked to 10 EDA interacting partners, retrieved from the STRING database. We found a novel biomarker CD68 by molecular docking analysis, suggesting all five EDA variants had lower affinity for EDAR, EDA2R, and CD68, implying that they would affect embryonic signaling between the ectodermal and mesodermal cell layers. In silico research such as gene ontology, subcellular localization, protein–protein interaction, and PTMs investigations indicates major functional alterations would occur in EDA variants. According to molecular simulations, EDA variants influence the structural conformation, compactness, stiffness, and function of the EDA protein. Further studies on cell line and animal models might be useful in determining their specific roles in functional annotations.
Solvent free synthesis of amidoalkyl derivatives under green and convenient conditions
Authors: Sadeghi Seyyed Hojjat , Moradi Leila
Published: November 2021

Amidoalkyl derivatives are significant compounds due to their application in the preparation of potent drugs and important biological compounds. In this context, we presented a new method for the synthesis of amido alkyl β‐naphthol and amidoalky naphthoquinones using ascorbic acid (vitamin C) as a natural and water‐soluble catalyst under solvent‐free conditions. Short reaction time, high yield of product, easy workup and low cost of catalyst are some of the advantages of this method. All the products were obtained in high to excellent yields and characterized by 1HNMR, 13CNMR, and FT‐IR methods.
Establishing reference sequences for each clade of SARS‐CoV‐2 to provide a basis for virus variation and function research
Authors: Yu Jian , Sun Shanshan , Tang Qianqian , Wang Chengzhuo , Yu Liangchen , Ren Lulu , Li Jun , Zhang Zhenhua
Published: November 2021

Coronavirus disease 2019 (COVID‐19) is a severe respiratory disease caused by the highly infectious severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2). As the COVID‐19 pandemic continues, mutations of SARS‐CoV‐2 accumulate. These mutations may not only make the virus spread faster, but also render current vaccines less effective. In this study, we established a reference sequence for each clade defined using the GISAID typing method. Homology analysis of each reference sequence confirmed a low mutation rate for SARS‐CoV‐2, with the latest clade GRY having the lowest homology with other clades (99.89%–99.93%), and the homology between other clade being greater than or equal to 99.95%. Variation analyses showed that the earliest genotypes S, V, and G had 2, 3, and 3 characterizing mutations in the genome respectively. The G‐derived clades GR, GH, and GV had 5, 6, and 13 characterizing mutations in the genome respectively. A total of 28 characterizing mutations existed in the genome of the latest clades GRY. In addition, we found differences in the geographic distribution of different clades. G, GH, and GR are popular in the USA, while GV and GRY are common in the UK. Our work may facilitate the custom design of antiviral strategies depending on the molecular characteristics of SARS‐CoV‐2.
Association of polymorphisms in tumor necrosis factors with SARS‐CoV‐2 infection and mortality rate: A case‐control study and in silico analyses
Authors: Heidari Nia Milad , Rokni Mohsen , Mirinejad Shekoufeh , Kargar Maryam , Rahdar Sara , Sargazi Saman , Sarhadi Mohammad , Saravani Ramin
Published: November 2021

The present coronavirus disease 2019 (COVID‐19) is spreading rapidly and existing data has suggested a number of susceptibility factors for developing a severe course of the disease.  The current case‐control experiment is aimed to study the associations of genetic polymorphisms in tumor necrosis factors (TNFs) with COVID‐19 and its mortality rate. A total of 550 participants (275 subjects and 275 controls) were enrolled. The tetra‐amplification refractory mutation system polymerase chain reaction technique was recruited to detect −308G>A TNFα and +252A>G TNFβ polymorphisms among the Iranian subjects. We demonstrated that carriers of the G allele of TNFβ‐252A/G, rs909253 A>G were more frequent in COVID‐19 subjects compared to the healthy group and this allele statistically increased the disease risk (odds ratio [OR] = 1.55, 95% confidence interval [CI] = 1.23–1.96, p < 0.0001). At the same time, the A allele of TNFα‐311A/G, rs1800629 G>A moderately decreased the risk of COVID‐19 (OR = 0.68, 95% CI = 0.53–0.86, p < 0.002). Also, we analyzed the various genotypes regarding the para‐clinical and disorder severity; we found that in the AA genotype of TNFβ‐252A/G (rs909253 A>G), the computed tomography scan pattern was different in comparison to cases carrying the AG genotype with p1 < 0.001. In addition, in the severe cases of COVID‐19, leukocyte and neutrophil count and duration of intensive care unit hospitalization in the deceased patients were significantly increased (p < 0.001). Moreover, the TNFα‐311A/G (rs1800629 G>A) variant is likely to change the pattern of splicing factor sites. Our findings provided deep insights into the relationship between TNFα/TNFβ polymorphisms and severe acute respiratory syndrome coronavirus 2. Replicated studies may give scientific evidence for exploring molecular mechanisms of COVID‐19 in other ethnicities.
Impact of the COVID‐19 lockdown in urgent pacemaker implantations: A cross‐sectional study
Authors: de Almeida Fernandes Diogo , Cadete Rúben , António Natália , Ventura Miguel , Cristóvão João , Elvas Luís , Gonçalves Lino
Published: November 2021

Aims

The COVID‐19 pandemic resulted in a decrease in patients' follow‐up and interventions with cardiovascular disease. In Portugal, the consequences on emergent pacemaker implantation rates are largely unknown. We sought to analyze the impact of the COVID‐19 pandemic on emergent pacemaker implantation rate and patient profile.

Methods

We retrospectively reviewed the clinical profile of the 180 patients who had pacemakers implanted in our hospital in an emergent setting from March 18, 2020, to May 17, 2020 (“lockdown”) and May 19 to July 17, 2020 (“postlockdown”). This data was then directly compared to the homologous periods from the year before.

Results

Urgent pacemaker implantation rates during "lockdown" was lower than its homologous period (−23.7%), and cases in "postlockdown" were significantly increased (+106.9% vs. "lockdown"; +13.2% vs. May–July 2019).

When comparing “lockdown” and “postlockdown,” there was a tendency for a higher number of temporary pacemaker use (p = .076). Patients during “lockdown” were 7.57 times more likely to present with hypotension/shock (odds ratio 7.57; p = .013). We also noted a higher tendency for hypotension on presentation during “lockdown” (p = .054) in comparison to 2019. In comparison to its homologous 2019 period, “postlockdown” saw more patients presenting with bradycardia (p = .026). No patients were admitted to the emergency department during "lockdown" for anomalies detected on ambulatory tests.

Conclusion

Our data show that the COVID‐19 pandemic had a real impact on urgent pacemaker implantation. Patients with bradyarrhythmias are at particular risk for severe complications and should seek medical care regardless of the pandemic.
Bottom‐up redistribution of biomass optimizes energy allocation, water use and yield formation in dryland wheat improvement
Authors: Li Pu‐Fang , Ma Bao‐Luo , Guo Sha , Ding Tong‐Tong , Xiong You‐Cai
Published: November 2021

BACKGROUND

Modern wheat cultivars have been developed having distinct advantages in many aspects under drought stress, such as plasticity in biomass allocation and root system architecture. A better understanding of the biomass allocation mechanisms that enable modern wheat to achieve higher yields and yield‐based water use efficiency (WUEg) is essential for implementing best management strategies and identifying phenotypic traits for cultivar improvement. We systematically investigated the biomass allocation, morphological and physiological characteristics of three ploidy wheat genotypes under 80% and 50% field water‐holding capacity (FC) conditions. Some crucial traits were also assessed in a complementary field experiment.

RESULTS

The diploid and tetraploid genotypes were found to allocate more biomass to the root system, especially roots in the topsoil under drought stress. Our data illustrated that lower WUEg and yield of these old genotypes were due to excessive investment in the root system, which was associated with severely restricted canopy development. Modern hexaploid genotypes were found to allocate smaller biomass to roots and larger biomass to shoots. This not only ensured the necessary water uptake, but also allowed the plant to distribute more assimilates and limited water to the shoots. Therefore, the hexaploid genotypes have evolved a stable plant canopy structure to optimize WUEg and grain yield.

CONCLUSION

This study demonstrated that the biomass shift from below ground to above ground or a more balanced root:shoot ratio tended to optimize water use and yield of the modern cultivars. This discovery provides potential guidance for future dryland wheat breeding and sustainable management strategies. © 2021 Her Majesty the Queen in Right of Canada Journal of The Science of Food and Agriculture © 2021 Society of Chemical Industry. Reproduced with the permission of the Minister of Agriculture and Agri‐Food Canada.
Simultaneous determination of isoxaflutole and its two metabolites in corn under field conditions by LC–MS/MS
Authors: Lan Feng , Li Qingyu , Sun Lin , Yu Weizhong , Jiang Wei , Wang Zhixin , Liu Chuande
Published: November 2021

OBJECTIVE

An improved QuEChERS method was established and verified for simultaneous determination of isoxaflutole and its metabolites diketonitrile and benzoic acid analogue residues in corn and plants. This method was mainly used to study the digestion rule and final residue level of isoxaflutole and its metabolites in corn and plants. It was hoped that the safe use of isoxaflutole in corn can be achieved eventually.

METHOD

The method was completed by means of ultra‐performance liquid chromatography with triple quadrupole mass spectrometry. The extraction of the target substance was through acetonitrile solution containing 1% acetic acid, and the purification was through primary secondary amine, octadecylsilane and graphitized carbon black sorbent.

RESULTS

In the method, the quantitative limits and detection limits of the three analytes were 0.005–0.01 and 0.001–0.003 mg kg−1 respectively. The half‐life of isoxaflutole in the plants in Shandong and Anhui was 36.4 and 42.1 days respectively, and the digestion dynamics all conformed to the first‐order kinetics. The final residues of isoxaflutole in green corn and mature corn were less than 0.02 mg kg−1 of the maximum residue limit set by the Codex Alimentarius Commission.

CONCLUSIONS

The residual amount of isoxaflutole in corn and plants at harvest time was acceptable when isoxaflutole was applied once at a dose of 121.5 g a.i. ha−1. © 2021 Society of Chemical Industry.
Effective extraction of tylosin and spiramycin from fermentation broth using thermo‐responsive ethylene oxide/propylene oxide aqueous two‐phase systems
Authors: Yang Ting , Zheng Ting , Wang Yan , Zhang Yan , He Dong , Zeng Hainan , Wei Yanli , Chen Xi , Wan Junfen , Cao Xuejun
Published: November 2021

Recyclable aqueous two‐phase systems with thermo‐responsive phase‐forming materials have been employed to separate macromolecules; however, these systems have achieved very limited separation efficiency for small molecules, such as antibiotics. In this study, aqueous two‐phase systems composed of the ethylene oxide/propylene oxide copolymer and water were developed to extract alkaline antibiotics from the fermentation broth. In the aqueous two‐phase systems with an ethylene oxide ratio of 20 and propylene oxide ratio of 80, the partition coefficients of tylosin and spiramycin reached 16.87 and 20.39, respectively, while the extraction recoveries were 70.67 and 86.70%, respectively. Coupled with mechanism analysis, we demonstrated the feasibility of extracting alkaline antibiotics using this aqueous two‐phase system, especially for 16‐membered macrolide antibiotics. The molecular dynamic simulation was employed to visualize the process of dual‐phase formation and the partition behavior of antibiotics in an aqueous two‐phase system. The dynamic simulation revealed the binding energy between the antibiotic and ethylene oxide/propylene oxide copolymers, which provides a simple indicator for screening suitable antibiotics in aqueous two‐phase systems. Our recyclable aqueous two‐phase systems provide a robust approach for the extraction of 16‐membered macrolide antibiotics with ease of operation and high recovery rates, which is appropriate for large‐scale extraction in the fermentation industry.
Rapid characterization of the constituents in Jigucao capsule using ultra high performance liquid chromatography with quadrupole time‐of‐flight mass spectrometry
Authors: Li Taiping , Zhang Mengli , Tan Zhien , Miao Jianhua , He Yanmei , Zhang Aihua , Ou Min , Huang Danna , Wu Fangfang , Wang Xijun
Published: November 2021

Jigucao capsule is a well‐known Chinese patent medicine for the treatment of acute and chronic hepatitis and cholecystitis. The chemical components of Jigucao capsule were not clear resulting from the paucity of relevant studies, which hindered the research of the pharmacological mechanism, the comprehensive development, and utilization of Jigucao capsule in clinical studies. By establishing a high‐throughput ultra‐performance liquid chromatography quadrupole time of flight mass spectrometry in combination with intelligent UNIFI software data processing platform to automatically characterize and identify the chemical profile of Jigucao capsule, 144 compounds were determined rapidly, including 34 terpenoids, 25 flavonoids, 22 steroids, 21 phenylpropanoids, 10 glycosides, six alkaloids, 13 organic acids, and other 13 components. These compounds may be the active components of Jigucao capsule. In this study, a rapid and robust method for comprehensively analyzing the chemical composition of Jigucao capsule was described and established for the first time. The results will provide a reference for the quality control of Jigucao capsule and the establishment of a higher quality standard, as well as for the pharmacodynamic material basis research.
Extraction of parabens by melamine sponge with determination by high‐performance liquid chromatography
Authors: Li Jingkang , Jiang Yanxiao , Sun Ying , Wang Xinghua , Ma Pinyi , Song Daqian , Fei Qiang
Published: November 2021

In the present study, we propose a novel method for the extraction of parabens in personal care products. A new, simple adsorptive material was obtained by combining metal‐organic frameworks and melamine sponges using the adhesive property of polyvinylidene fluoride. This new material, metal‐organic frameworks/melamine sponges, was found to be particularly suitable for solid‐phase extraction. The structural characteristics of metal‐organic frameworks/melamine sponges were first analyzed by scanning electron microscopy. Subsequently, solid‐phase extraction was performed on sample solutions, and the extracted substances were then analyzed by high‐performance liquid chromatography. Following optimization of important experimental conditions, excellent recovery rates were obtained. Our novel method was then applied to the extraction of four parabens (methylparahydroxybenzoates, ethylparahydroxybenzoates, propylparahydroxybenzoates, and butylparahydroxybenzoates) from real samples. The results yielded limits of detection of 0.26–0.41 ng/mL. The inter‐ and intra‐day recoveries were 104.0–109.7% and 91.2–98.1%, respectively (relative standard deviation, <13.8%).
Preliminary Clinical Outcomes of VOIS‐Implant in Patients With Unilateral Vocal Fold Paralysis
Authors: Hsieh Li‐Chun , Chen Chin‐Kuo , Chang Chin‐Wen , Leu Yi‐Shing , Ho Guan‐Min
Published: November 2021

Objectives/Hypothesis

Evaluation of the clinical outcomes after 6 months of treatment with a novel adjustable implant, the APrevent® Vocal‐Implant‐System (VOIS), in conjunction with medialization thyroplasty (MT) in patients with unilateral vocal fold paralysis.

Study Design

Prospective case series study at single tertiary referral center.

Methods

Preoperative and 1 week, 7 weeks, and 6 months postoperative glottal efficiency (maximum phonation time [MPT]), voice quality (including GRBAS‐scores and acoustic parameters) and self‐perceived voice‐related handicap (voice handicap index [VHI‐30]) were measured and analyzed, whereas type of vocal fold closure was evaluated and determined by flexible videolaryngoscopy based on Södersten and Lindestad classification (Wilcoxon signed‐rank test).

Results

Thirteen patients underwent MT with VOIS under local anesthesia. Six months after surgery, the VHI‐30 and MPT had improved from a preoperative mean of 75.0 ± 22.9 and 2.7 ± 2.1 s to a postoperative mean of 20.6 ± 19.7 and 6.3 ± 4.0 s, respectively. The mean GRBAS score improved from preoperative scores of Gpreop = 2.7, Rpreop = 2.6, Bpreop = 2.6, Apreop = 2.2, and Spreop = 2.0 to Gpostop = 0.3, Rpostop = 0.3, Bpostop = 0.2, Apostop = 0.2, and Spostop = 0.3 at 6 months postoperatively. Improved glottal closure was achieved in all patients (n = 13). Five patients received postoperative adjustment for the optimization of voice quality and glottal closure. No intra‐ or postoperative complications were observed. Significant improvements in acoustic parameters, including percentage jitter, percentage shimmer, and signal‐to‐noise ratio, were also observed after MT. All results were statistically significant (P < .05, Cohen's d > .8).

Conclusions

APrevent® VOIS‐Implantation is a safe procedure with good voice outcomes. Postoperative adjustments can be performed smoothly to optimize voice quality and glottal closure.

Level of Evidence

3 Laryngoscope, 132:1622–1629, 2022
Enabling Technologies for Obtaining Desired Stiffness Gradients in GelMA Hydrogels Constructs
Authors: Sauty Bastien , Santesarti Gianluca , Fleischhammer Tabea , Lindner Patrick , Lavrentieva Antonina , Pepelanova Iliyana , Marino Michele
Published: November 2021

This work presents enabling technologies for the optimization of the manufacturing of GelMA‐based hydrogels constructs with desired stiffness gradients. The manufacturing technique combines dynamic mixing for gradient generation and a passive micromixer for efficient hydrogel blending. A digital replica of the fabrication process is developed, integrating theoretical and computational models, as well as experimental data, in order to predict and control the stiffness profile obtained within the constructs. The workflow for the development of the in silico framework, based on rigorous verification, validation, and uncertainty quantification steps, is presented. The validation of the digital replica is based on reference settings of process variables, which result in constructs with an exponential stiffness profile. The developed in silico model has been employed for optimizing process variables in order to obtain a linear stiffness profile in the extruded construct without the need of expensive and time‐consuming trial‐and‐error procedures. The developed digital replica is now a powerful tool for the creation of hydrogel gradient constructs for tissue engineering applications or for the screening of optimal 3D cell culture conditions.
Fusion‐Induced Growth of Biomimetic Polymersomes: Behavior of Poly(dimethylsiloxane)‐Poly(ethylene oxide) Vesicles in Saline Solutions Under High Agitation
Authors: Marušič Nika , Zhao Ziliang , Otrin Lado , Dimova Rumiana , Ivanov Ivan , Sundmacher Kai
Published: November 2021

Giant unilamellar vesicles serve as membrane models and primitive mockups of natural cells. With respect to the latter use, amphiphilic polymers can be used to replace phospholipids in order to introduce certain favorable properties, ultimately allowing for the creation of truly synthetic cells. These new properties also enable the employment of new preparation procedures that are incompatible with the natural amphiphiles. Whereas the growth of lipid compartments to micrometer dimensions has been well established, growth of their synthetic analogs remains underexplored. Here, the influence of experimental parameters like salt type/concentration and magnitude of agitation on the fusion of nanometer‐sized vesicles made of poly(dimethylsiloxane)‐poly(ethylene oxide) graft copolymer (PDMS‐g‐PEO) is investigated in detail. To this end, dynamic light scattering, microscopy, and membrane mixing assays are employed, and the process at different time and length scales is analyzed. This optimized method is used as an easy tool to obtain giant vesicles, equipped with membrane and cytosolic biomachinery, in the presence of salts at physiological concentrations.
A CT‐less approach to quantitative PET imaging using the LSO intrinsic radiation for long‐axial FOV PET scanners
Authors: Teimoorisichani Mohammadreza , Panin Vladimir , Rothfuss Harold , Sari Hasan , Rominger Axel , Conti Maurizio
Published: November 2021

Purpose

Long‐axial field‐of‐view (FOV) positron emission tomography (PET) scanners have gained a lot of interest in the recent years. Such scanners provide increased sensitivity and enable unique imaging opportunities that were not previously feasible. Benefiting from the high sensitivity of a long‐axial FOV PET scanner, we studied a computed tomography (CT)–less reconstruction algorithm for the Siemens Biograph Vision Quadra with an axial FOV of 106 cm.

Methods

In this work, the background radiation from radioisotope lutetium‐176 in the scintillators was used to create an initial estimate of the attenuation maps. Then, joint activity and attenuation reconstruction algorithms were used to create an improved attenuation map of the object. The final attenuation maps were then used to reconstruct quantitative PET images, which were compared against CT‐based PET images. The proposed method was evaluated on data from three patients who underwent a flurodeoxyglucouse PET scan.

Results

Segmentation of the PET images of the three studied patients showed an average quantitative error of 6.5%–8.3% across all studied organs when using attenuation maps from maximum likelihood estimation of attenuation and activity and 5.3%–6.6% when using attenuation maps from maximum likelihood estimation of activity and attenuation correction coefficients.

Conclusions

Benefiting from the background radiation of lutetium‐based scintillators, a quantitative CT‐less PET imaging technique was evaluated in this work.
Technical note: Experimental determination of the effective point of measurement of the PTW‐31010 ionization chamber in proton and carbon ion beams
Authors: Barna Sandra , Resch Andreas Franz , Puchalska Monika , Georg Dietmar , Palmans Hugo
Published: November 2021

Purpose

The accurate knowledge of the effective point of measurement (Peff) is particularly important for measurements in proximity to high dose gradients such as in the distal fall‐off of particle beams. For plane‐parallel ionization chambers (ICs), Peff is well known and located at the center of the inner surface of the entrance window. For cylindrical ICs, Peff is shifted from the chamber's center toward the beam source. According to IAEA TRS‐398, this shift can be calculated as 0.75·rcyl for light ions with rcyl being the radius of the cavity. For proton beams and in absence of a dose gradient, no shift is recommended. We have experimentally determined Peff for the 0.125 cc Semiflex IC in both proton and carbon ion beams.

Methods

The first method consisted of simultaneous irradiation of a plane‐parallel IC and the Semiflex in a 4‐cm wide spread‐out Bragg peak. In the second method, a single‐energy beam was used, and both ICs were positioned successively at the same measurement depths. For both approaches, the shift of the distal edge of the depth ionization distributions recorded by the two chambers at different reference points was used to calculate Peff of the Semiflex. Both methods were applied in carbon ion beams, and only the latter was applied in proton beams.

Results

Both methods yielded a similar Peff for carbon ions, 0.88·rcyl, and 0.84·rcyl, which results in a difference of only 0.1 mm. The difference to the recommended value of 0.75·rcyl is 0.4 and 0.3 mm, respectively, which is larger than the positioning uncertainty. In the proton beam, a Peff of 0.92·rcyl was obtained.

Conclusions

The Peff for the 0.125 cc Semiflex IC is shifted further from the cavity center as recommended by IAEA TRS‐398 for light ions, with the shift for proton beams being even larger than for carbon ion beams.
Theoretical studies on the g factors, optical absorption, and their concentration variations for Mo5+ in 40PbO–(10 − x)Y2O3–50P2O5:xMoO3 glass
Authors: Zhou Hong‐Fei , Dong Hui‐Ning , Wang Yi‐Ming , Liu Xu‐Sheng
Published: November 2021

On the basis of the higher order perturbation formulas of g factors for a 4d1 group in tetragonally compressed octahedra, the g factors, optical absorption, local structure, and their concentration dependences of pentavalent molybdenum in 40PbO–(10 − x)Y2O3–50P2O5:xMoO3 (1 ≤ x ≤ 5 mol%) glass are uniformly investigated. The experimental optical absorption spectra and g factors for Mo5+ at various concentrations x are reasonably regenerated by using the reasonable exponential concentration functions of the cubic field parameter Dq, covalent factor N, and relative tetragonal compression ratio ρ. The tetragonal compression ratio ρ due to the Jahn–Teller effect was found in the range of 3.8% to 4.2%. The decreasing trend of Dq and N and the increasing trend of ρ with concentration can be interpreted as the fact that the variations of MoO3 and Y2O3 concentrations lead to the modulations of local structure and electron cloud distribution around Mo5+, associated with the adjustment of the glass network. The concentration dependence of optical basicity is also analyzed for the above glass systems.