bluuebunny/crossref_metadata_2025 huggingface dataset:
Doping‐Induced Viscoelasticity in PbTe Thermoelectric Inks for 3D Printing of Power‐Generating Tubes
Authors: Lee Jungsoo , Choo Seungjun , Ju Hyejin , Hong Jaehyung , Yang Seong Eun , Kim Fredrick , Gu Da Hwi , Jang Jeongin , Kim Gyeonghun , Ahn Sangjoon , Lee Ji Eun , Kim Sung Youb , Chae Han Gi , Son Jae Sung
Published: April 2021

Thermoelectric (TE) technologies offer promising means to enhance fossil energy efficiencies by generating electricity from waste heat from industrial or automobile exhaust gases. For these applications, thermoelectric modules should be designed from the perspective of system integration for efficient heat transfer, system simplification, and low processing cost. However, typical thermoelectric modules manufactured by traditional processes do not fulfil such requirements, especially for exhaust pipes. Hence, a 3D‐printing method for PbTe thermoelectric materials is reported to design high‐performance power‐generating TE tubes. The electronic doping‐induced surface charges in PbTe particles are shown to significantly improve the viscoelasticities of inks without additives, thereby enabling precise shape and dimension engineering of 3D bulk PbTe with figures of merit of 1.4 for p‐type and 1.2 for n‐type materials. The performance of the power‐generating TE tube fabricated from 3D‐printed PbTe tubes is demonstrated experimentally and computationally as an effective strategy to design system‐adaptive high‐performance thermoelectric generators.
Comparative effectiveness and safety of anticoagulants for the treatment of heparin‐induced thrombocytopenia
Authors: Nilius Henning , Kaufmann Jonas , Cuker Adam , Nagler Michael
Published: April 2021

Background

The effectiveness and safety of non‐heparin anticoagulants for the treatment of heparin‐induced thrombocytopenia (HIT) are not fully established, and the optimal treatment strategy is unknown. In a systematic review and meta‐analysis, we aimed to determine precise rates of platelet recovery, new or progressive thromboembolism (TE), major bleeding, and death for all non‐heparin anticoagulants and to study potential sources of variability.

Methods

Following a detailed protocol (PROSPERO: CRD42020219027), EMBASE and Medline were searched for all studies reporting clinical outcomes of patients treated with non‐heparin anticoagulants (argatroban, danaparoid, fondaparinux, direct oral anticoagulants [DOAC], bivalirudin, and other hirudins) for acute HIT. Proportions of patients with the outcomes of interest were pooled using a random‐effects model for each drug. The influence of the patient population, the diagnostic test used, the study design, and the type of article was assessed.

Results

Out of 3194 articles screened, 92 studies with 119 treatment groups describing 4698 patients were included. The pooled rates of platelet recovery ranged from 74% (bivalirudin) to 99% (fondaparinux), TE from 1% (fondaparinux) to 7% (danaparoid), major bleeding from 1% (DOAC) to 14% (bivalirudin), and death from 7% (fondaparinux) to 19% (bivalirudin). Confidence intervals were mostly overlapping, and results were not influenced by patient population, diagnostic test used, study design, or type of article.

Discussion

Effectiveness and safety outcomes were similar among various anticoagulants, and significant factors affecting these outcomes were not identified. These findings support fondaparinux and DOACs as viable alternatives to conventional anticoagulants for treatment of acute HIT in clinical practice.
Synthesis of 2‐Aryl‐(3‐Organochalcogenyl)Thieno[2,3‐b]Pyridines Promoted by Oxone®
Authors: Peglow Thiago J. , Bartz Ricardo H. , Barcellos Thiago , Schumacher Ricardo F. , Cargnelutti Roberta , Perin Gelson
Published: April 2021

We describe herein an alternative method for the synthesis of 2‐aryl‐(3‐organochalcogenyl)thieno[2,3‐b]pyridines through the electrophilic cyclization of 3‐(arylethynyl)‐2‐(alkylthio)pyridines promoted by electrophilic species of organochalcogen compounds. These species were generated in situ by the oxidative cleavage of chalcogen‐chalcogen (Se, Te) bond of diorganyl dichalcogenides using Oxone® in ethanol as solvent in an open‐flask at 78 °C. The protocol allowed the synthesis of highly substituted thieno[2,3‐b]pyridines starting from several diorganyl dichalcogenides and 3‐(arylethynyl)‐2‐(alkylthio)pyridines, obtaining 21 new compounds in good to excellent yields (70–99%). Still, the method showed good efficiency on the gram‐scale synthesis. In addition, several synthetic transformations such as oxidation, selenylation and hydrogenation reactions were demonstrated.
Regenerable Radical‐Trapping and Preventive Selenazolonamine Antioxidants
Authors: Kumar Manish , Yadav Manisha , Chhillar Babli , Singh Vijay P.
Published: April 2021

Selenazolonamines 10 a–d with free amine (‐NH2) group, a new series of preventive and radical‐trapping antioxidants were synthesized from their corresponding diselenides. The radical‐trapping antioxidant capacity of compounds 10 a–d was determined in a chlorobenzene/water membrane‐like model system in which azo‐initiated peroxidation of linoleic acid was carried out in the lipid phase. The regeneration occurred in the aqueous ascorbic acid as co‐antioxidant, which could regenerate the antioxidants and enhance their inhibition times. The best antioxidant 10 d substituted with para‐NMe2 a strong electron‐donating group quenched the peroxyl radicals more efficiently than α‐tocopherol almost 5.5‐fold longer inhibition time. The novel selenazolonamines 10 a–d and their derivatives exhibited good preventive i. e. glutathione peroxidase‐like activity in the coupled reductase assay. Based on 77Se NMR spectroscopy, a catalytic cycle for 10 d, involving diselenide, selenosulfide, and selenol as intermediates was proposed. The mechanism for quenching of peroxyl radicals for 10 d was also considered to be involved via proton‐coupled electron transfer reaction.
Photo‐Induced Arylation of Carbazoles With Aryldiazonium Salts
Authors: Maeda Bumpei , Mori Genki , Sakakibara Yota , Yagi Akiko , Murakami Kei , Itami Kenichiro
Published: April 2021

Arylcarbazoles have been widely used in materials science as important organic semiconductor molecules. To investigate the electronic and photophysical properties of arylcarbazole with different substitution patterns, facile and straightforward synthesis of arylcarbazole derivatives is sought after. Herein we report on photo‐induced direct arylation reactions of carbazole. Treatment of carbazoles with aryldiazonium salts afforded the arylated carbazole. Although the reaction was not regioselective, C1 and C4‐arylated carbazoles were obtained as the major isomers. When N‐pyridylcarbazole was employed as the substrate with palladium catalyst, the reaction proceeded selectively at C1 position.
Katalytische Oxygenierung von Kohlenwasserstoffen durch Mono‐μ‐oxo‐Dikupfer(II)‐Spezies erzeugt durch O‐O‐Spaltung von tetranuklearen CuI/CuII‐Peroxo‐Komplexen
Authors: Jurgeleit Ramona , Grimm‐Lebsanft Benjamin , Flöser Benedikt Maria , Teubner Melissa , Buchenau Sören , Senft Laura , Hoffmann Jonas , Naumova Maria , Näther Christian , Ivanović‐Burmazović Ivana , Rübhausen Michael , Tuczek Felix
Published: April 2021

Eine der Herausforderungen der Katalyse ist die Transformation inerter C‐H‐Bindungen in nützliche Produkte. Kupferhaltige Monooxygenasen spielen hier eine wichtige Rolle. Wir zeigen, dass die Tieftemperatur‐Oxygenierung zweikerniger Kupfer(I)‐Komplexe zu tetranuklearen, gemischtvalenten μ4‐Peroxo‐[CuI/CuII]2‐Komplexen führt. Diese Cu4O2‐Intermediate erfahren eine irreversible, thermisch aktivierte O‐O‐Bindungsspaltung, wobei Cu2O‐Komplexe entstehen, die eine stark exotherme H‐Atom‐Abstraktion von Kohlenwasserstoffen, gekoppelt an einen O‐Transfer, katalysieren. Die Cu2O‐Spezies können auch mit N2O erzeugt werden, was ihr Potential zur Aktivierung kleiner Moleküle zeigt. Die Bindung und Spaltung von O2, die zu den primären Cu4O2‐Intermediaten bzw. ‐Komplexen führt, wird mit lösungsspektroskopischen Methoden und Massenspektrometrie aufgeklärt. Die Reaktivitäten dieser Spezies etablieren ein neues, zu 100 % atomökonomisches Szenario für die katalytische, kupfervermittelte Monooxygenierung organischer Substrate, bei dem beide O‐Atome von O2 eingebaut werden.
pH‐Amplified CRET Nanoparticles for In Vivo Imaging of Tumor Metastatic Lymph Nodes
Authors: Wang Zenghui , Xia Heming , Chen Binlong , Wang Yaoqi , Yin Qingqing , Yan Yue , Yang Ye , Tang Mingmei , Liu Jianxiong , Zhao Ruiyang , Li Wenzhe , Zhang Qiang , Wang Yiguang
Published: April 2021

Noninvasive imaging strategies have been extensively investigated for in vivo mapping of sentinel lymph nodes (SLNs). However, the current imaging strategies fail to accurately assess tumor metastatic status in SLNs with high sensitivity. Here we report pH‐amplified self‐illuminating near‐infrared nanoparticles, which integrate chemiluminescence resonance energy transfer (CRET) and signal amplification strategy, enabling accurate identification of metastatic SLNs. After draining into lymph nodes, the nanoparticles were phagocytosed and dissociated in acidic phagosomes of inflammatory macrophages to emit near‐infrared luminescent light. Using these nanoparticles, we successfully differentiated tumor metastatic lymph nodes from benign ones. These nanoparticles also exhibited excellent imaging capability for early detection of metastatic SLNs in diverse animal tumor models with small tumor volume (100–200 mm3).
ZW800‐PEG: A Renal Clearable Zwitterionic Near‐Infrared Fluorophore for Potential Clinical Translation
Authors: Yang Chengeng , Wang Haoran , Yokomizo Shinya , Hickey Morgan , Chang Hyejin , Kang Homan , Fukuda Takeshi , Song Mi Young , Lee Sang Yeul , Park Jin Woo , Bao Kai , Choi Hak Soo
Published: April 2021

Near‐infrared (NIR) fluorescence imaging has advanced medical imaging and image‐guided interventions during the past three decades. Despite tremendous advances in imaging devices, surprisingly only a few dyes are currently available in the clinic. Previous fluorophores, ZW800‐1A and ZW800‐1C, significantly improved the poor performance of the FDA‐approved indocyanine green. However, ZW800‐1A is not stable in serum and ZW800‐1C induces severe stacking in aqueous media. To solve such dilemmas, ZW800‐PEG was designed by introducing a flexible yet stable thiol PEG linker. ZW800‐PEG shows high solubility in both aqueous and organic solvents, thus improving renal clearance with minimal binding to serum proteins during systemic circulation. The sulfide group on the meso position of the heptamethine core improves serum stability and physicochemical properties including the maximum emission wavelength shift to 800 nm, enabling the use of ZW800‐PEG for image‐guided interventions and augmenting photothermal therapy.
Iron‐Catalyzed Wacker‐type Oxidation of Olefins at Room Temperature with 1,3‐Diketones or Neocuproine as Ligands**
Authors: Puls Florian , Linke Philipp , Kataeva Olga , Knölker Hans‐Joachim
Published: April 2021

Herein, we describe a convenient and general method for the oxidation of olefins to ketones using either tris(dibenzoylmethanato)iron(III) [Fe(dbm)3] or a combination of iron(II) chloride and neocuproine (2,9‐dimethyl‐1,10‐phenanthroline) as catalysts and phenylsilane (PhSiH3) as additive. All reactions proceed efficiently at room temperature using air as sole oxidant. This transformation has been applied to a variety of substrates, is operationally simple, proceeds under mild reaction conditions, and shows a high functional‐group tolerance. The ketones are formed smoothly in up to 97 % yield and with 100 % regioselectivity, while the corresponding alcohols were observed as by‐products. Labeling experiments showed that an incorporated hydrogen atom originates from the phenylsilane. The oxygen atom of the ketone as well as of the alcohol derives from the ambient atmosphere.
Oxygen‐Linked Cyclopentadienyl Rhodium(III) Complexes‐Catalyzed Asymmetric C−H Arylation of Benzo[h]quinolines with 1‐Diazonaphthoquinones
Authors: Pan Chongqing , Yin Si‐Yong , Wang Shao‐Bo , Gu Qing , You Shu‐Li
Published: April 2021

Chiral cyclopentadienyl rhodium (CpRh) complex‐catalyzed asymmetric C−H functionalization reactions have witnessed a significant progress in organic synthesis. In sharp contrast, the reported chiral Cp ligands are limited to C‐linked Cp and are often synthetically challenging. To address these issues, we have developed a novel class of tunable chiral cyclopentadienyl ligands bearing oxygen linkers, which were efficient catalysts for C−H arylation of benzo[h]quinolines with 1‐diazonaphthoquinones, affording axially chiral heterobiaryls in excellent yields and enantioselectivity (up to 99 % yield, 98.5:1.5 er). Mechanistic studies suggest that the reaction is likely to proceed by electrophilic C−H activation, and followed by coupling of the cyclometalated rhodium(III) complex with 1‐diazonaphthoquinones.
Highly Stable Single Crystals of Three‐Dimensional Porous Oligomer Frameworks Synthesized under Kinetic Conditions
Authors: Hou Linxiao , Shan Chuan , Song Yanpei , Chen Sifan , Wojtas Lukasz , Ma Shengqian , Sun Qi , Zhang Lin
Published: April 2021

Various robust, crystalline, and porous organic frameworks based on in situ‐formed imine‐linked oligomers were investigated. These oligomers self‐assembled through collaborative intermolecular hydrogen bonding interactions via liquid–liquid interfacial reactions. The soluble oligomers were kinetic products with multiple unreacted aldehyde groups that acted as hydrogen bond donors and acceptors and directed the assembly of the resulting oligomers into 3D frameworks. The sequential formation of robust covalent linkages and highly reversible hydrogen bonds enforced long‐range symmetry and facilitated the production of large single crystals, with structures that were unambiguously determined by single‐crystal X‐ray diffraction. The unique hierarchical arrangements increased the steric hindrance of the imine bond, which prevented attacks from water molecules, greatly improving the stability. The multiple binding sites in the frameworks enabled rapid sequestration of micropollutant in water.
Development of Continuous Flow Systems to Access Secondary Amines Through Previously Incompatible Biocatalytic Cascades**
Authors: Mattey Ashley P. , Ford Grayson J. , Citoler Joan , Baldwin Christopher , Marshall James R. , Palmer Ryan B. , Thompson Matthew , Turner Nicholas J. , Cosgrove Sebastian C. , Flitsch Sabine L.
Published: April 2021

A key aim of biocatalysis is to mimic the ability of eukaryotic cells to carry out multistep cascades in a controlled and selective way. As biocatalytic cascades get more complex, reactions become unattainable under typical batch conditions. Here a number of continuous flow systems were used to overcome batch incompatibility, thus allowing for successful biocatalytic cascades. As proof‐of‐principle, reactive carbonyl intermediates were generated in situ using alcohol oxidases, then passed directly to a series of packed‐bed modules containing different aminating biocatalysts which accordingly produced a range of structurally distinct amines. The method was expanded to employ a batch incompatible sequential amination cascade via an oxidase/transaminase/imine reductase sequence, introducing different amine reagents at each step without cross‐reactivity. The combined approaches allowed for the biocatalytic synthesis of the natural product 4O‐methylnorbelladine.
Enantioselective Total Synthesis of Berkeleyone A and Preaustinoids
Authors: Zhang Yang , Ji Yunpeng , Franzoni Ivan , Guo Chuning , Jia Hongli , Hong Benke , Li Houhua
Published: April 2021

Herein we report the first enantioselective total synthesis of 3,5‐dimethylorsellinic acid‐derived meroterpenoids (−)‐berkeleyone A and its five congeners ((−)‐preaustinoids A, A1, B, B1, and B2) in 12–15 steps, starting from commercially available 2,4,6‐trihydroxybenzoic acid hydrate. Based upon the recognition of latent symmetry within D‐ring, our convergent synthesis features two critical reactions: 1) a symmetry‐breaking, diastereoselective dearomative alkylation to assemble the entire carbon core, and 2) a Sc(OTf)3‐mediated sequential Krapcho dealkoxycarbonylation/carbonyl α‐tert‐alkylation to forge the intricate bicyclo[3.3.1]nonane framework. We also conducted our preliminary biomimetic investigations and uncovered a series of rearrangements (α‐ketol, α‐hydroxyl‐β‐diketone, etc.) responsible for the biomimetic diversification of (−)‐berkeleyone A into its five preaustinoid congeners.
Large‐Area Crystalline Zeolitic Imidazolate Framework Thin Films
Authors: Chen Zhi , Wang Rui , Ma Tao , Wang Jin‐Long , Duan Yu , Dai Zhi‐Zhan , Xu Jie , Wang Hui‐Juan , Yuan Jiayin , Jiang Hai‐Long , Yin Yue‐Wei , Li Xiao‐Guang , Gao Min‐Rui , Yu Shu‐Hong
Published: April 2021

We report that continuous MOF films with highly controlled thickness (from 44 to 5100 nm) can be deposited over length scales greater than 80 centimeters by a facile, fast, and cost‐effective spray‐coating method. Such success relies on our discovery of unprecedented perfectly dispersed colloidal solutions consisting of amorphous MOF nanoparticles, which we adopted as precursors that readily converted to the crystalline films upon low‐temperature in situ heating. The colloidal solutions allow for the fabrication of compact and uniform MOF films on a great deal of substrates such as fluorine‐doped tin oxide, glass, SiO2, Al2O3, Si, Cu, and even flexible polycarbonate, widening their technological applications where substrates are essential. Despite the present work focuses on the fabrication of uniform cobalt‐(2‐methylimidazole)2 and zinc‐(2‐methylimidazole)2 films, our findings mark a great possibility in producing other high‐quality MOF thin films on a large scale.
Polysulfates Block SARS‐CoV‐2 Uptake through Electrostatic Interactions**
Authors: Nie Chuanxiong , Pouyan Paria , Lauster Daniel , Trimpert Jakob , Kerkhoff Yannic , Szekeres Gergo Peter , Wallert Matthias , Block Stephan , Sahoo Anil Kumar , Dernedde Jens , Pagel Kevin , Kaufer Benedikt B. , Netz Roland R. , Ballauff Matthias , Haag Rainer
Published: April 2021

Here we report that negatively charged polysulfates can bind to the spike protein of SARS‐CoV‐2 via electrostatic interactions. Using a plaque reduction assay, we compare inhibition of SARS‐CoV‐2 by heparin, pentosan sulfate, linear polyglycerol sulfate (LPGS) and hyperbranched polyglycerol sulfate (HPGS). Highly sulfated LPGS is the optimal inhibitor, with an IC50 of 67 μg mL−1 (approx. 1.6 μm). This synthetic polysulfate exhibits more than 60‐fold higher virus inhibitory activity than heparin (IC50: 4084 μg mL−1), along with much lower anticoagulant activity. Furthermore, in molecular dynamics simulations, we verified that LPGS can bind more strongly to the spike protein than heparin, and that LPGS can interact even more with the spike protein of the new N501Y and E484K variants. Our study demonstrates that the entry of SARS‐CoV‐2 into host cells can be blocked via electrostatic interactions, therefore LPGS can serve as a blueprint for the design of novel viral inhibitors of SARS‐CoV‐2.
Lewis Base–Brønsted Acid–Enzyme Catalysis in Enantioselective Multistep One‐Pot Syntheses
Authors: Mantel Marvin , Giesler Markus , Guder Marian , Rüthlein Elisabeth , Hartmann Laura , Pietruszka Jörg
Published: April 2021

Establishing one‐pot, multi‐step protocols combining different types of catalysts is one important goal for increasing efficiency in modern organic synthesis. In particular, the high potential of biocatalysts still needs to be harvested. Based on an in‐depth mechanistic investigation of a new organocatalytic protocol employing two catalysts {1,4‐diazabicyclo[2.2.2]octane (DABCO); benzoic acid (BzOH)}, a sequence was established providing starting materials for enzymatic refinement (ene reductase; alcohol dehydrogenase): A gram‐scale access to a variety of enantiopure key building blocks for natural product syntheses was enabled utilizing up to six catalytic steps within the same reaction vessel.
Coating the Right Polymer: Achieving Ideal Metal–Organic Framework Particle Dispersibility in Polymer Matrixes Using a Coordinative Crosslinking Surface Modification Method
Authors: Li Conger , Liu Junhong , Zhang Kexin , Zhang Songwei , Lee Yongjin , Li Tao
Published: April 2021

This work describes the first generalizable method to modify various metal–organic framework (MOF) surfaces with polyimide, polysulfone, polycarbonate, and polymer of intrinsic microporosity‐1 (PIM‐1). The method first utilizes electrostatic adsorption to rapidly decorate positively charged MOF surfaces with a layer of negatively charged metal‐organic nanocapsule, PgC5Cu. After mixing with the polymer, the copper open metal sites on PgC5Cu can coordinatively crosslink the polar functional groups on the surface polymer upon thermal activation thereby resulting in the immobilization of a uniform sub‐10 nm polymer coating. We quantitatively analyzed the distribution of free path spacing between MOF particles and demonstrated that when the surface polymer matches the matrix polymer, the MOF dispersion was not only visually improved but also found to align perfectly with a theoretically predicted ideal dispersion model where no aggregation driving force was present.
Impact behavior of aminosilane functionalized nanosilica based shear thickening fluid impregnated Kevlar fabrics
Authors: Katiyar Ajay , Nandi Tandra , Prasad N. Eswara
Published: April 2021

In the present work, two types of shear thickening fluids have been synthesized by using neat and aminosilane functionalized silica nanoparticles and their viscosity curves have been obtained by the rheometer. Based on the values of peak viscosity of synthesized shear thickening fluids, the surface functionalized nanosilica based shear thickening fluid has been chosen as a best candidate due to the high viscosity for impregnation into the neat Kevlar of different layers viz. four (04) and eight (08) layers for velocity impact study. The experimental investigations reveal high energy absorption of shear thickening fluid impregnated Kevlar as compared to the neat Kevlar. The maximum energy absorption 62 J is achieved corresponding to the initial velocity 154 m∙s−1 for 08 layers shear thickening fluid impregnated Kevlar specimen. The data have also been analytically determined and validated with the experimental data. The experimental data have good agreement with the analytical data within the accuracy of around 15 to 20%. The present findings can have significant inferences towards the fabrication of shear thickening fluids using nanomaterials for numerous applications such as soft armors, dampers, nanofinishing and so forth.
Transcriptomic analysis of diapause‐associated genes in Exorista civilis Rondani (Diptera:Tachinidae)
Authors: Zhang Bo , Han Hai‐Bin , Xu Lin‐Bo , Li Yan‐Ru , Song Mi‐Xia , Liu Ai‐Ping
Published: April 2021

Exorista civilis Rondani (Diptera:Tachinidae) is an excellent dominant parasitic enemy all over the world. But there has been a lack of research on the molecular regulation of diapause in E. civilis. To investigate the important diapause‐associated genes and metabolic pathways in E. civilis, we can provide a theoretical basis for clarifying the molecular mechanism of diapause at the transcriptome level. The Illumina HiSeq. 2000 platform was used to perform transcriptome sequencing and bioinformatics analysis of the non‐diapause and diapause pupae of E. civilis. 58,050 unigenes were successfully assembled, in which 4355 upregulated and 3158 downregulated unigenes were differentially expressed. Moreover, by Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichments, 896 kinds of the differentially expressed genes were specifically analyzed and showed that diapause‐associated genes were related to be involved in the pathways of cold resistance, amino acid metabolism, and energy metabolism. Furthermore, these upregulated five genes showed the same trends of expression patterns between quantitative real‐time polymerase chain reaction and RNA‐Seq. This study provides a theoretical basis for the further study of the diapausing molecular mechanisms of E. civilis.
Induction of diapause by clock proteins period and timeless via changes in PTTH and ecdysteroid titer in the sugar beet moth, Scrobipalpa ocellatella (Lepidoptera: Gelechiidae)
Authors: Ahmadi Fatemeh , Mikani Azam , Moharramipour Saeid
Published: April 2021

The sugar beet moth, Scrobipalpa ocellatella (Boyd), one of the most severe sugar beet pests, causes quantitative and qualitative yield losses late in the autumn. Previously, it was shown that low temperature and short‐day photoperiod together cause diapause induction in pupae. Here, the interaction of the critical elements of the diapause induction, including the period (PER), timeless (TIM), prothoracicotropic hormone (PTTH), and ecdysteroid titer, were investigated. Immunohistochemistry results showed that the number of period immunoreactivity (PER‐ir) and TIM‐ir cells in nondiapause pupae (NDP) was lower than in the brain of the diapause pupae (DP). Moreover, the number of PER‐ir and TIM‐ir cells in the protocerebrum and optic lobe (OL) of NDP was lower than DP. Moreover, lower PTTH content in the brain and hemolymph of DP was confirmed by competitive enzyme‐linked immunosorbent assay. Enzyme immunoassay showed a lower 20‐hydroxyecdysone (20E) titer in the hemolymph of the DP compared with the NDP. Within a short‐day condition, PER and TIM titers increased in the brain leading to decreasing PTTH titers in the brain and hemolymph that caused decreasing 20E titer in the hemolymph, leading to the induction of diapause. This study suggests that PER and TIM could be one of the brain factors that play an essential role in regulating diapause in S. ocellatella.
Dynamics of heat shock protein responses to thermal stress changes after metamorphosis in a lepidopteran insect
Authors: Su Yaozong , Li Xiangrui , Zhang Wei , Zhang Bo , Ma Chun‐Sen
Published: April 2021

In the last decade, unexpected high temperatures have been frequent in spring and early summer. Numerous studies have shown that such thermal stress has substantial effects on life‐history traits that influence fitness of insects, but few have examined expression dynamics of heat shock proteins (Hsps) across developmental stages, especially as regards potential carry‐over effects at the transcriptional level across metamorphosis. We exposed pupae of the oriental fruit moth (“OFM,” Grapholita molesta Busck) to mild heat stress (38°C, 6 h) and then quantified expression patterns of six Hsps (Hsp90, 70, 60, 40, 21, and 11) from pupal through adult stages. Almost all Hsps showed a higher expression immediately after pupae were heat‐stressed, but later dropped to normal levels after metamorphosis. Although upregulation of Hsps is transient and the effects carry over longer to early adult stage, upregulation will nonetheless have positive effects on adult fitness. The fitness of some insects may benefit from higher expression of chaperon genes after mild stress, in the form of higher fecundity and longer lifespan, as a carry‐over effect. These results suggest that mild thermal stress can change genetic expression that later boosts adult fitness through a cascade effect.
Development, validation, and application of a simple UPLC–MS/MS method for simultaneous quantification of five traditional antipsychotics in human plasma
Authors: Fan Liju , An Jing , Cui Yanjun , Dong Zhanjun
Published: April 2021

A UPLC–MS/MS method was developed to determine the levels of five traditional antipsychotics (APs) (chlorprothixene, perphenazine, fluphenazine, thioridazine, and promethazine) in human plasma with carbamazepine as the internal standard. Samples were extracted using simple liquid–liquid extraction (ethyl acetate/methyl tert‐butyl ether, 2:3 v/v); then the analytes were subjected to gradient elution chromatography with a mobile phase composed of 0.1% formic acid in water and acetonitrile. The analytes were separated using a Waters XBridge BEH C18 column (100 × 2.1 mm, 2.5 μm). The linear ranges of chlorprothixene, perphenazine, fluphenazine, thioridazine, and promethazine are 2–250 ng/mL, r > 0.995. The limit of quantitation is 2 ng/mL, and the limit of detection is in the range of 0.1–0.5 ng/mL. The inter‐day and intra‐day relative standard deviations are less than 10%, and the relative errors are in the range of −5.70 to 7.20%. The recoveries of the five drugs are in the range of 70–109%. The results of methodology verification indicate that this method is simple, economical, sensitive, and suitable for the simultaneous quantification of five traditional APs in human plasma.
Advanced teaching method for learning power system operation based on load flow simulations
Authors: Honrubia‐Escribano Andrés , Villena‐Ruiz Raquel , Artigao Estefanía , Gómez‐Lázaro Emilio , Morales Ana
Published: April 2021

Current power systems are undergoing a rapid and complex transformation due to the integration of distributed generation. Load flow analysis is increasingly necessary to evaluate not only the operating point of the existing power system but also the design of future expansions. There are a wide variety of power system analysis packages used for load flow analysis. Of these, PowerFactory, one of the tools most widely used by network operators, is implemented for the present learning approach. In fact, one of the challenges for electric utility companies is the lack of experts who are familiar with this type of commercial tool. In the present work, several scenarios were defined and implemented using PowerFactory, covering common real‐life situations in power systems, such as the connection of a new line or a capacitor bank, or the installation of a renewable energy power plant. In this regard, the goal of the present teaching method was to complement the educational competences of power system engineers. As such, the proposed method was implemented in both an Electrical Engineering Degree course and a Master's Degree course in Industrial Engineering, where useful application feedback from students was obtained. Furthermore, the proposed approach is easily replicable for teaching/learning activities at other academic institutions.
Did court find professor's workplace wasn't hostile?
Authors: Lyerly Eric
Published: April 2021

The University of Tennessee hired an Indian‐born sociologist as a tenure‐track assistant professor on its faculty. The university warned the professor several times in her annual retention reviews that her publishing work was unsatisfactory, in both quality and quantity. However, the professor's publications continued to fall short of departmental standards. Accordingly, the university decided not to retain her in 2014. The professor's employment ended the next year.
Building consumer communal relationships through cause‐related marketing: From the perspective of persuasion knowledge
Authors: Song Baobao , Tao Weiting , Wen Taylor Jing
Published: April 2021

This study investigates the value of cause‐related marketing (CRM) campaigns in consumer relationship management. Specifically, following the tenets of persuasion knowledge model and equity theory, this study proposes that the effect of consumers' inferences of companies' manipulative intent (IMI) in CRM campaigns on consumer–brand communal relationships is contingent on consumers' knowledge about the degree to which the companies and the social cause benefit from the campaigns. A panel of 506 U.S. consumers was recruited to complete an online survey. Results reveal that when consumers believe that nonprofit partners benefit more from a CRM campaign than the company does, IMI positively affects consumer–brand communal relationships. However, when consumers perceive greater corporate benefits than social benefits, IMI negatively affects consumer–brand communal relationships. These results present a convincing case that in order to cultivate a long‐term communal relationship with consumers, companies should promote their CRM programs by highlighting these programs' social benefits and impact. If such programs are considered to yield more corporate benefits, companies should make efforts to mitigate the negative impact that IMI may bring to consumer–brand communal relationships. This study also advances our existing understanding of communal relationships and CRM by unveiling how CRM‐related factors collectively influence corporate building of a long‐term communal relationship with consumers. We hope to inspire future researchers who are interested in bridging CRM and communal relationship literature to inform effective CRM practice.
In‐hospital outcomes after transcatheter edge‐to‐edge mitral valve repair in patients with chronic kidney disease: An analysis from the 2010–2016 National inpatient sample
Authors: Panchal Hemang B. , Stone Gregg W. , Saxena Anshul , Bursac Zoran , Veledar Emir , Nagabandi Arun , Davidson Charles J. , Leon Martin B. , Beohar Nirat
Published: April 2021

Objectives

To assess the outcomes following transcatheter edge‐to‐edge mitral valve repair (TMVr) in patients with chronic kidney disease (CKD).

Background

Percutaneous TMVr is beneficial in high surgical risk patients with severe mitral regurgitation (MR). However, those with CKD are not well studied.

Methods

Utilizing the International Classification of Disease (ninth and tenth revision, clinical modification codes) and the Nationwide Inpatient Sample database, we identified 9,228 patients who underwent TMVr during 2010–2016, including those with no or mild CKD (group 1, n = 6,654 [72.11%]), moderate or severe CKD (group 2, n = 2,125 [23.03%]) and end‐stage renal disease (ESRD) on dialysis (group 3, n = 449 [4.86%]). In‐hospital clinical outcomes, length of stay and cost were assessed.

Results

In‐hospital mortality increased numerically as CKD severity increased, but not statistically different between groups (1.8, 3.3, and 4.5% respectively in group 1, 2, and 3, p = .07). Moderate to severe CKD (group 2) was an independent predictor of acute renal failure requiring hemodialysis (ARFD) (OR: 3.51, CI: 2.33–5.28, p < .0001), the composite outcome of death, ARFD or stroke [OR: 3.15, 95% CI: 2.10–4.76, p < .0001] and extended length of stay [OR: 1.73, 95% CI: 1.24–2.42), p = .001] while ESRD (group 3) was an independent predictor of higher hospital cost [OR: 1.66, 95% CI: 1.01–2.74), p = .04] as compared with no or mild CKD (group 1).

Conclusions

High surgical risk patients with severe MR commonly have associated comorbidities including CKD. TMVr outcomes appear to worsen with worsening CKD and therefore careful clinical case selection and further studies evaluating TMVr outcomes in CKD patients is warranted.
Conductive Metal‐Organic Frameworks: Electronic Structure and Electrochemical Applications
Authors: Nath Akashdeep , Asha K. S. , Mandal Sukhendu
Published: April 2021

Smarter and minimization of devices are consistently substantial to shape the energy landscape. Significant amounts of endeavours have come forward as promising steps to surmount this formidable challenge. It is undeniable that material scientists were contemplating smarter material beyond purely inorganic or organic materials. To our delight, metal‐organic frameworks (MOFs), an inorganic‐organic hybrid scaffold with unprecedented tunability and smart functionalities, have recently started their journey as an alternative. In this review, we focus on such propitious potential of MOFs that was untapped over a long time. We cover the synthetic strategies and (or) post‐synthetic modifications towards the formation of conductive MOFs and their underlying concepts of charge transfer with structural aspects. We addressed theoretical calculations with the experimental outcomes and spectroelectrochemistry, which will trigger vigorous impetus about intrinsic electronic behaviour of the conductive frameworks. Finally, we discussed electrocatalysts and energy storage devices stemming from conductive MOFs to meet energy demand in the near future.
Chiral‐at‐Iron Catalyst for Highly Enantioselective and Diastereoselective Hetero‐Diels‐Alder Reaction
Authors: Hong Yubiao , Cui Tianjiao , Ivlev Sergei , Xie Xiulan , Meggers Eric
Published: April 2021

This study demonstrates that chiral‐at‐iron complexes, in which all coordinated ligands are achiral and the overall chirality the consequence of a stereogenic iron center, are capable of catalyzing asymmetric transformations with very high enantioselectivities. The catalyst is based on a previously reported design (J. Am. Chem. Soc. 2017, 139, 4322), in which iron(II) is surrounded by two configurationally inert achiral bidentate N‐(2‐pyridyl)‐substituted N‐heterocyclic carbenes in a C2‐symmetric fashion and complemented by two labile acetonitriles. By replacing mesityl with more bulky 2,6‐diisopropylphenyl substituents at the NHC ligands, the steric hindrance at the catalytic site was increased, thereby providing a markedly improved asymmetric induction. The new chiral‐at‐iron catalyst was applied to the inverse electron demand hetero‐Diels‐Alder reaction between β,γ‐unsaturated α‐ketoester and enol ethers provide 3,4‐dihydro‐2H‐pyrans in high yields with excellent diastereoselectivities (up to 99 : 1 dr) and excellent enantioselectivities (up to 98 % ee). Other electron rich dienophiles are also suitable as demonstrated for a reaction with a vinyl azide.
Solvent‐Dependent Stabilization of a Charge Transfer State is the Key to Ultrafast Triplet State Formation in an Epigenetic DNA Nucleoside
Authors: Wang Xueli , Martínez‐Fernández Lara , Zhang Yuyuan , Zhang Kun , Improta Roberto , Kohler Bern , Xu Jianhua , Chen Jinquan
Published: April 2021

2’‐Deoxy‐5‐formylcytidine (5fdCyd), a naturally occurring nucleoside found in mammalian DNA and mitochondrial RNA, exhibits important epigenetic functionality in biological processes. Because it efficiently generates triplet excited states, it is an endogenous photosensitizer capable of damaging DNA, but the intersystem crossing (ISC) mechanism responsible for ultrafast triplet state generation is poorly understood. In this study, time‐resolved mid‐IR spectroscopy and quantum mechanical calculations reveal the distinct ultrafast ISC mechanisms of 5fdCyd in water versus acetonitrile. Our experiment indicates that in water, ISC to triplet states occurs within 1 ps after 285 nm excitation. PCM‐TD‐DFT computations suggest that this ultrafast ISC is mediated by a singlet state with significant cytosine‐to‐formyl charge‐transfer (CT) character. In contrast, ISC in acetonitrile proceeds via a dark 1nπ* state with a lifetime of ∼3 ps. CT‐induced ISC is not favored in acetonitrile because reaching the minimum of the gateway CT state is hampered by intramolecular hydrogen bonding, which enforces planarity between the aldehyde group and the aromatic group. Our study provides a comprehensive picture of the non‐radiative decay of 5fdCyd in solution and new insights into the factors governing ISC in biomolecules. We propose that the intramolecular CT state observed here is a key to the excited‐state dynamics of epigenetic nucleosides with modified exocyclic functional groups, paving the way to study their effects in DNA strands.
Kinetic and thermodynamic modelling of thermal decomposition of bitumen under high pressure enhanced with simulated annealing and artificial intelligence
Authors: Alade Olalekan , Gang Lei , Tariq Zeeshan , Mahmoud Mohamed , Al Shehri Dhafer , Sultan Abdullah , Al‐Ramadhan Ammar , Mokheimer Esmail
Published: April 2021

Thermogravimetric analysis (TGA) of energy resources including bitumen provides kinetic parameters, which can be applied in design and simulation of processes for thermal recovery and conversion. In this investigation, pressurized non‐isothermal decomposition of bitumen under inert environment has been studied. The kinetic parameters were calculated at different pressures (0.1, 0.5, and 1 MPa) and heating rates (10, 20, and 30°C/min) using the differential method. The parameters were later optimized using simulated annealing (SA) optimization algorithm. The results were subsequently validated by comparing the predicted conversion (α) with those of artificial neural network (ANN). Thermodynamic parameters (enthalpy, entropy, and Gibb's free energy) were also calculated using the optimized kinetic parameters. The TGA results show that weight loss and thermal conversion decreased as the total pressure increased from 0.1–1 MPa, at all heating rates. Conversely, the thermal conversion rate (dα/dT) was observed to first decrease with increasing pressure (0.1–1 MPa) within the low temperature oxidation (LTO) and fuel deposition (FD) regions. In contrast, it increased with increasing total pressure within the high temperature oxidation (HTO) region. Furthermore, it was observed that the activation energy (Ea) increased with increasing pressures at all heating rates, while the frequency factor (A) was independent of the pressure or the heating rates. In addition, the thermodynamic parameters tend to increase with increasing pressure. Ultimately, the results established that the SA algorithm could be used to enhance the performance of the differential modelling method in calculating kinetic parameters and predicting the conversion.
Simultaneous removal of elemental mercury and NO from flue gas by the CeO2/TiO2 catalysts and the mechanism investigation
Authors: He Zhong , Long Yifei , Liu Wenjie , Li Xiaoyi , Wang Yuan , Hu Jiangjun
Published: April 2021

Mercury pollution has become one of the high‐profile environmental problems in the world. A series of CeyTi catalyst were synthesized by sol–gel method, and the process of simultaneous conversion of NO and removal of mercury (Hg0) in the flue gas was studied. BET, SEM, and XRD were used to systematically detect the physicochemical properties of the catalysts, which show that excessive Ce loading would make its specific surface area reduce. The NO conversion efficiency would increase with the increase of the Ce loading. The optimal Ce/Ti mass ratio was 0.3. A part of the adsorbed NO would be oxidized by the active oxygen species on the catalyst surface to produce a certain amount of nitrogen‐containing substances, such as NO+, NO3−, or NO2. The produced substances could promote the adsorption and oxidation of Hg0. The NO conversion was very dependent on the oxygen in the flue gas. The activity of the Ce0.3Ti catalyst was promoted in the presence of O2. SO2 and H2O would inhibit the reaction of NO conversion and Hg0 removal. The mechanisms of the catalytic system have been proved via the Mars‐Maessen mechanism.
Prebiotic Chemistry in Aqueous Environment: A Review of Peptide Synthesis and Its Relationship with Genetic Code
Authors: Ying Jianxi , Ding Ruiwen , Liu Yan , Zhao Yufen
Published: April 2021

Prebiotic peptide synthesis and the origin of the genetic code are central issues concerning the origin of life. The question of how they are possibly correlated on the primordial Earth remains perplexing, although numerous experiments have been carried out to explain the prebiotic chemistry of peptide synthesis and the genetic code origin. The purpose of this article is to review the chemical reactions occurred during the synthesis of peptides and the origin of the genetic code in the early Earth aqueous environment. Meanwhile, we attempt to review their relationship as well. At last, from our perspective, the chiral properties of biomolecules should be taken into account in the prebiotic chemical scenarios, which may contribute to some breakthroughs in the further research of this field.
Understanding the Potential In Vitro Modes of Action of Bis(β‐diketonato) Oxovanadium(IV) Complexes
Authors: Sergi Baris , Bulut Ipek , Xia Ying , Waller Zoë A. E. , Yildizhan Yasemin , Acilan Ceyda , Lord Rianne M.
Published: April 2021

To understand the potential in vitro modes of action of bis(β‐diketonato) oxovanadium(IV) complexes, nine compounds of varying functionality have been screened using a range of biological techniques. The antiproliferative activity against a range of cancerous and normal cell lines has been determined, and show these complexes are particularly sensitive against the lung carcinoma cell line, A549. Annexin V (apoptosis) and Caspase‐3/7 assays were studied to confirm these complexes induce programmed cell death. While gel electrophoresis was used to determine DNA cleavage activity and production of reactive oxygen species (ROS), the Comet assay was used to determine induced genomic DNA damage. Additionally, Förster resonance energy transfer (FRET)‐based DNA melting and fluorescent intercalation displacement assays have been used to determine the interaction of the complexes with double strand (DS) DNA and to establish preferential DNA base‐pair binding (AT versus GC).
Transgenic‐based solutions for citrus disease management in Argentina
Authors: De Francesco Agustina , Sendín Lorena Noelia , Gómez Rocío Liliana , Reyes Carina Andrea
Published: April 2021

Citrus is a major fruit crop with economic importance worldwide, with citriculture historically threatened at times by a diverse array of pathogens. As a leading producer and exporter, Argentina has been dealing with endemic and quarantine diseases of citrus by implementing conventional management strategies. In recent decades, the pursuit of pathogen‐resistant transgenic citrus has been explored in the country as part of a long‐term and sustainable disease management strategy. Successful genetically modified organisms (GMOs) were created locally, engineered to resist viruses and bacteria for the control of tristeza, psorosis, canker, and huanglongbing diseases of citrus. Although the Argentine regulatory system accommodated these developments, there were also difficulties that demand further recognition and analysis. In the present work, we describe four major diseases affecting Argentine citriculture and a series of GMO‐oriented strategies for their management. We explore the methodologies behind these strategies, including transgenic‐based approaches, the current state of regulations, and what further actions may be taken to ensure continuing protection for citriculture.
Zero‐voltage switching half‐bridge pulse width modulation DC–DC converter with switched capacitor active snubber cell for renewable energy applications
Authors: Bodur Haci , Yesilyurt Huseyin , Ting Naim Suleyman , Sahin Yakup
Published: April 2021

In this paper, soft switching isolated half‐bridge converter with a new active snubber cell that uses switched capacitor for renewable energy applications is proposed. The proposed snubber cell does not consist any magnetic element so that its structure is quite simple. Furthermore, the auxiliary switches in the proposed active snubber cell are exposed to only half of the input voltage. There is no additional voltage and current stress on any semiconductor devices. All semiconductor power devices in the proposed converter are operated by soft switching. The proposed converter is analyzed thoroughly, and the theoretical analyzes are affirmed by an implementation having 300‐VDC input, 20‐VDC output, 75‐W output power, and 150‐kHz switching frequency. The overall hard switching efficiency of the converter is increased from 86.4% to 92.9% by aid of the proposed soft switching snubber cell.