bluuebunny/crossref_metadata_2025_split huggingface dataset:
Incorporation and Utility of a Responsive Ribonucleoside Analogue in Probing the Conformation of a Viral RNA Motif by Fluorescence and 19F NMR Spectroscopy
Authors: Manna Sudeshna , Sontakke Vyankat A. , Srivatsan Seergazhi G. 
Published: November 2021

AbstractDevelopment of versatile probes that can enable the study of different conformations and recognition properties of therapeutic nucleic acid motifs by complementing biophysical techniques can greatly aid nucleic acid analysis and therapy. Here, we report the design, synthesis and incorporation of an environment‐sensitive ribonucleoside analogue, which serves as a two‐channel biophysical platform to investigate RNA structure and recognition by fluorescence and 19F NMR spectroscopy techniques. The nucleoside analogue is based on a 5‐fluorobenzofuran‐uracil core and its fluorescence and 19F NMR chemical shifts are highly sensitive to changes in solvent polarity and viscosity. Notably, the modified ribonucleotide and phosphoramidite substrates can be efficiently incorporated into RNA oligonucleotides (ONs) by in vitro transcription and standard solid‐phase ON synthesis protocol, respectively. Fluorescence and 19F readouts of the nucleoside incorporated into model RNA ONs are sensitive to the neighbouring base environment. The responsiveness of the probe was aptly utilized in detecting and quantifying the metal ion‐induced conformational change in an internal ribosome entry site RNA motif of hepatitis C virus, which is an important therapeutic target. Taken together, our probe is a good addition to the nucleic acid analysis toolbox with the advantage that it can be used to study nucleic acid conformation and recognition simultaneously by two biophysical techniques.
PEGylated Poly‐HDACi: A Designer Polyprodrug from Optimized Drug Units**
Authors: Han Jinghua , Wang Da‐Yuan , Wang Qiuyu , Meng Li , Luo Zihan , Li Jing , Kang Yanke , Lv Wenhui , Huang Qingqing , Wang Peng George , Wang Yajie , Shen Jie , Wang Yanming 
Published: November 2021

AbstractWe designed, synthesized, and characterized a tri‐block copolymer. Its hydrophobic part, a chain of histone deacetylase inhibitor (HDACi) prodrug, was symmetrically flanked by two identical PEG blocks, whereas the built‐in HDACi was a linear molecule, terminated with a thiol at one end, and a hydroxyl group at the other. Such a feature facilitated end‐to‐end linkage of prodrugs through alternatively aligned disulfides and carbonates. The disulfides served dual roles: redox sensors of smart nanomedicine, and warheads of masked HDACi drugs. This approach, carefully designed to benefit both control‐release and efficacy, is conceptually novel for optimizing drug units in nanomedicine. Micelles from this designer polyprodrug released only PEG, CO2 and HDACi, and synergized with DOX against HCT116 cells, demonstrating its widespread potential in combination therapy. Our work highlights, for the first time, the unique advantage of thiol‐based drug molecules in nanomedicine design.
Catalytic Reduction of Oximes to Hydroxylamines: Current Methods, Challenges and Opportunities
Authors: Mas‐Roselló Josep , Cramer Nicolai 
Published: November 2021

AbstractCatalytic reduction of oximes represents a direct efficient approach to synthesize valuable hydroxylamine derivatives. However this transformation presents significant challenges: oximes are hard to reduce and, if reactive, reductive cleavage of the weak N−O bond often leads to primary amine side products. The first suitable systems involved the use of platinum‐based heterogeneous catalysts with hydrogen as reductant and stoichiometric amounts of a strong Brønsted acid. More recently metal‐free and transition‐metal‐based homogeneous catalysts have been developed, which display the highest turnovers (up to 4000). In the asymmetric variants, the E/Z‐geometry of the oxime double bond affects significantly the stereoselectivity, sometimes requiring extra synthetic efforts in substrate preparation. This minireview provides an overview of the advances and limitations in catalytic oxime to hydroxylamine reduction. Emphasis is put on highlighting and comparing the practical aspects of the existing methods, such as their reaction conditions and substrate scope. Additionally, future directions for improving this young research area are suggested.
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

AbstractElaboration 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

AbstractMethane 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

AbstractThe 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

AbstractInvited 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

AbstractA 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

AbstractMechanochemistry 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

AbstractThe 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

AbstractWhile 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

AbstractThe 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

AbstractFerrocene 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

AbstractA 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

Abstract
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

Abstract

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

Abstract
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