bluuebunny/crossref_metadata_2025 huggingface dataset:
The Synthesis of Hexaazatrinaphthylene‐Based 2D Conjugated Copper Metal‐Organic Framework for Highly Selective and Stable Electroreduction of CO2 to Methane
Authors: Liu Yanze , Li Shuai , Dai Lu , Li Jiani , Lv Jianning , Zhu Zhejiaji , Yin Anxiang , Li Pengfei , Wang Bo
Published: May 2021

2D conjugated MOFs have attracted significant interests in recent years owing to their special structural features and promising physical and chemical properties. These intriguing attributes, to a large extent, stem from the nature of incorporated ligands. The available ligands for the construction of 2D conjugated MOFs are still limited, especially those that have heteroatoms included and exposed to the pores. In this work, we designed and synthesized a highly symmetric hexaazatrinaphthylene (HATNA)‐based ligand with two different coordination sites. Through selective coordination, a highly crystalline and porous 2D conjugated copper metal‐organic framework was constructed. Due to the synergic effects of HATNA and copper catecholate node, this HATNA‐based 2D conjugated MOF can mediate the electrocatalytic reduction of CO2 to methane with high selectivity of 78 % at high current density of 8.2 milliamperes per square centimetre (mA cm−2) for long durability over 12 hours.
Synthesis and Multiple Subsequent Reactivity of Anionic cyclo‐E3 Ligand Complexes (E=P, As)
Authors: Piesch Martin , Reichl Stephan , Seidl Michael , Balázs Gábor , Scheer Manfred
Published: May 2021

A synthetic pathway for the synthesis of novel anionic sandwich complexes with a cyclo‐E3 (E=P, As) ligand as an end deck was developed giving [Cp′′′Co(η3‐E3)]− (Cp′′′=1,2,4‐tri‐tert‐butylcyclopentadienyl, E=P ([5]), As ([6])) in good yields suitable for further reactivity studies. In the reaction with the chlorophosphanes R2PCl (R=Ph, Cy, tBu), neutral complexes with a disubstituted cyclo‐E3P (E=P, As) ligand in [Cp′′′Co(η3‐E3PR2)] (E=P (7 a–c), As (9 a–c)) were obtained. These compounds can be partially or completely converted into complexes with a cyclo‐E3 (E=P, As) ligand with an exocyclic {PR2} unit in [Cp′′′Co(η2:η1‐E3PR2)] (E=P (8 a–c), As (10 a–c)). Additionally, the insertion of the chlorosilylene [LSiCl] (L=(tBuN)2CPh) into the cyclo‐E3 ligand of [5] and [6] was achieved and the novel heteroatomic complexes [Cp′′′Co(η3‐E3SiL)] (E=P (11), As (12)) could be isolated. The reaction pathway was elucidated by DFT calculations.
Chemoselective and ligand‐free aerobic oxidation of benzylic alcohols to carbonyl compounds using alumina‐supported mesoporous nickel nanoparticle as an efficient recyclable heterogeneous catalyst
Authors: Das Asit Kumar , Nandy Sneha , Bhar Sanjay
Published: May 2021

An economically efficient and operationally simple ligand‐free protocol for the chemoselective oxidation of benzylic alcohols to carbonyl compounds has been developed using alumina‐supported nickel nanoparticles as a stable recyclable heterogeneous catalyst along with potassium tert‐butoxide in the presence of aerial oxygen as an eco‐friendly oxidant. The aliphatic alcohols remained unaffected under the present condition. Excellent chemoselectivity has also been demonstrated through intermolecular and intramolecular competition experiments. This protocol accommodates a diverse range of substituents with the tolerance of various sensitive moieties during the reaction. The catalyst could be recovered by filtration and reused consecutively without any significant loss in the catalytic activity. Moreover, the heterogeneity of the catalyst has also been established by the “hot filtration method (Sheldon's test)”.
Pullulan/poly(N‐vinylimidazole) cryogel: An efficient adsorbent for methyl orange
Authors: Hezarkhani Marjan , Ustürk Selma , Özbilenler Cahit , Yilmaz Elvan
Published: May 2021

Pullulan/poly(N‐vinylimidazole) (PNVI) hybrid cryogels were synthesized under free radical polymerization and chemical crosslinking conditions in an alkaline, aqueous solution of pullulan (PUL), N‐vinylimidazole (NVI), ammonium persulfate and epicholorohydrin (ECH) at −18°C. PUL and PNVI cryogels alone were also synthesized under similar conditions. Optimum cryogel formation conditions were determined by considering product yields and gel fractions of the samples. The products were characterized by elemental analysis, FTIR‐ATR spectrometry, Thermal gravimetric analysis, and scanning electron microscopy (SEM) analyses. It has been found that PUL/PNVI hybrid samples bear improved physicochemical properties compared to ECH crosslinked PUL and PNVI samples alone. They act as hydrogels in aqueous medium reaching equilibrium swelling capacity values of the order of 600%. Dried PUL/PNVI cryogels show higher thermal stability than the dried cryogels of the parent polymers and maintain their physical integrity over a prolonged time period. Macroporous morphology was revealed by SEM analysis. Having 54.2 mg/g maximum equilibrium adsorption capacity in 200 ppm methyl orange solution and maintaining 95% of its adsorption capacity at the end of seven consecutive adsorption/desorption cycles, PUL/PNVI cryogel proved to be an efficient and durable dye adsorbent using methyl orange as the model compound in aqueous solution.
Exploration and reconstruction of a medieval harbour using hydroacoustics, 3‐D shallow seismic and underwater photogrammetry: A case study from Puck, southern Baltic Sea
Authors: Pydyn Andrzej , Popek Mateusz , Kubacka Maria , Janowski Łukasz
Published: May 2021

Exploration of the marine environment using underwater remote‐sensing methods is the most reasonable method for investigating submerged archaeological heritage sites, preserving their current condition and maintaining them for future generations. While non‐invasive recognition of heritage sites is one of the main objectives of underwater archaeology, the nearshore environment of the small Polish town of Puck hides one of the biggest medieval harbours in the Baltic Sea. The following research objectives were met in this study: (a) exploration of underwater archaeological heritage harbour in Puck using high‐resolution hydroacoustics, 3‐D shallow seismics and underwater photogrammetry; (b) reconstruction of the submerged Puck medieval port by the combining of hydroacoustics, 3D shallow seismics, underwater photogrammetry and archival documentation; (c) estimation of the rate at which the bottom sediments containing the archaeological objects are being destroyed. The underwater archaeological site of Puck harbour was explored using multiple surveying methods, including multibeam echosounder, parametric sub‐bottom profiler, underwater photogrammetry, aerial photography and comparison with archival documentation. Very high‐resolution bathymetry from a multibeam echosounder allowed seabed features such as piles, stones and horizontal structural elements to be identified, along with other archaeological artefacts, boat wrecks and boat‐building artefacts. The 3‐D shallow seismic datasets allowed us to distinguish, for example, several outcropping structures, a previously unknown buried shipwreck, past excavation trenches, the harbour boundary and a palaeochannel of the Płutnica River. Fusing datasets from multiple sources in the geographic information system (GIS) environment allowed for a combined visualization of the heritage sites, providing a broad archaeological demonstration of the underwater structure. By comparing with archival documentation, we calculated that 43% of biogenic layers containing archaeological objects eroded over 26 years. Our results demonstrated that without any doubt, underwater remote‐sensing methods are the most appropriate for exploration and investigation of underwater heritage sites while maintaining their original value.
A multiproxy approach to studying a large prehistoric enclosure in Ojców, Kraków Upland, Poland
Authors: Leloch Michał , Jakubczak Michał , Przybyła Marcin , Pyżewicz Katarzyna , Szeliga Marcin , Wojenka Michał , Czajka Grzegorz , Kot Małgorzata
Published: May 2021

Due to the presence of multiple caves and rock shelters as well as flint outcrops, Ojców Upland is a region with an exceptionally high concentration of prehistoric human settlement traces. It has attracted archaeologists for over 150 years, leading to what was considered to have been a proper prospection of the area. Nonetheless, the analysis of airborne laser scanning has recently brought surprising results. In the very centre of the upland, on the densely forested hill ‘Złota Góra’ (Golden Hill), the remains of an exceptionally large defensive structure in the form of several rows of embankments were found. The use of magnetic methods made it possible to confirm their anthropogenic origin and the likely type of embankment construction. In turn, the layout of embankments combined with the results of a surface survey and the analyses of the acquired artefacts and the settlement context speak in favour of linking this defensive structure with a high degree of probability with the Neolithic or Eneolithic, most likely the Lengyel‐Polgár cycle or Baden culture. The presence of such a large fortification in the immediate vicinity of flint mines could shed new light on the image of the Late Neolithic‐Early/Middle Eneolithic period in this part of Europe.
Bioconversion of waste sheep wool to microbial peptone by Bacillus licheniformisEY2
Authors: Tuysuz Elanur , Ozkan Hakan , Arslan Nazli P. , Adiguzel Ahmet , Baltaci Mustafa O. , Taskin Mesut
Published: May 2021

Peptones are among the most expensive culture components used in the cultivation of microorganisms. This study was performed to prepare a protein hydrolysate from sheep wool using a locally isolated keratinolytic bacterium Bacillus licheniformis EY2 (GenBank: MN809476), and to investigate the usability of the prepared hydrolysate as a peptone in a microbial medium. The optimum pH, temperature, and incubation time for wool hydrolysis and keratinolytic activity were determined as 7.0, 55 °C, and 6 days, respectively. Optimum concentrations of KH2PO4, MgSO4, and NaCl were determined as 1.5, 0.5, and 2 g/L, respectively. After the prepared hydrolysate was partially purified, it was converted to wool peptone (WP). The total protein, ash, carbohydrate, and lipid content of WP was found to be 82.7, 7.2, 0.1, and 0.2 g/100 g, respectively. Fourier transform infrared (FTIR) analysis of WP confirmed the formation of sulfoxide bonds (S=O), which indicated the breaking of disulfide bonds. When compared with commercial tryptone peptone (TP), WP was found to be superior for the cell growth performances of Esherichia coli, Bacillus subtilis, Staphylococcus aureus, Lactobacillus plantarum, Pediococcus pentosaceus, Candia albicans and Aspergillus niger. A protein hydrolysate (including wool protein hydrolysate) prepared via microbial hydrolysis was tested for the first time as a peptone source. The cost of WP is much lower than commercial peptones. At the same time, the method developed offers an environmentally friendly approach for the reduction of the amount of unutilized or waste sheep wool. © 2021 Society of Industrial Chemistry and John Wiley & Sons Ltd.
Impact of bio‐renewable energy sources on reduction of emission footprint from vehicles
Authors: Puškár Michal , Živčák Jozef , Kočišová Michaela , Šoltésová Marieta , Kopas Melichar
Published: May 2021

The transport sector generates up to one quarter of greenhouse gas emissions. Transport is also one of the main polluters in urban agglomerations. This has an impact on the quality of the environment and on human health. Road traffic emissions constitute up to 70% of the total emissions of the transport sector. The automotive industry is under growing pressure to reduce emissions significantly and to utilize alternative sources of energy, among which bio‐renewable sources play a very important role. An important task of scientific publications is to analyze the influence of fuels with different bio‐component content on the total emission footprint from vehicles and to evaluate the real contribution of bio‐components to environmental protection. The experiments reported here were conducted during the 13‐regimes testing cycle, which was especially developed for piston combustion engines. The results create a complex view of the generation of gaseous emissions, taking into consideration engine regimes and loading. © 2021 Society of Chemical Industry and John Wiley & Sons, Ltd
A new robust Bayesian small area estimation via ‐stable model for estimating the proportion of athletic students in California
Authors: Zarei Shaho , Arima Serena , Jona Lasinio Giovanna
Published: May 2021

In the last few years, diabetes mellitus and obesity revealed to be one of the fastest‐growing chronic diseases in youth in the United States. The number of new diabetes cases is dramatically increasing, and, for the moment, effective therapy does not exist. Experts believe that one of the causes of this increase is the decline in exercise behavior. The California Education Code requires local educational agencies (LEAs) to administer the FITNESSGRAM, the Physical Fitness Test (PFT), to Californian students of public schools. This test evaluates six fitness areas, and experts defined that a passing result on all six areas of the test represents a fitness level that offers some protection against the diseases associated with physical inactivity. We consider 2015–2016 data provided by the California Department of Education (CDE): for each Californian county (), we aim at estimating the county‐level proportion of students with a score equal to six. To account for the heterogeneity of the phenomenon and the presence of outlying counties, we extend the standard area‐level model by specifying the random effects as a symmetric ‐stable (SS) distribution that can accommodate different types of outlying observations. The model can accurately estimate the county‐level proportion of students with a score equal to six. Results highlight some interesting relationships with social and economic situations in each county. The performance of the proposed model is also investigated through an extensive simulation study.
An evaluation of the impact of stimulus mode on acquisition, maintenance, and generalization of tacts of actions
Authors: Mandel Natalie R. , Cividini‐Motta Catia , Schram Jeffrey
Published: May 2021

Individuals with an autism spectrum disorder or communication delay may experience deficits in tacting. Furthermore, children, with and without language impairments, acquire tacts of objects earlier than tacts of actions, suggesting that tacts of actions may be more difficult to learn (e.g., Sheng & McGregor, 2010). One variable that may impact acquisition of tacts of actions is the type of stimulus (e.g., picture of the action; video of the action) used during training. This study compared acquisition of tacts of actions taught using pictures, videos, and in vivo models. Data were also collected on generalization and maintenance of the acquired tacts as well as participant preference towards the stimulus mode used during tact training. All three participants acquired all tacts, independent of the stimulus mode used during training. However, tacts of actions taught using an in vivo model were acquired in fewer sessions and had greater generalization and maintenance outcomes. In addition, preference for a specific stimulus mode was idiosyncratic across participants.
Enhanced production of nonanedioic acid from nonanoic acid by engineered Escherichia coli
Authors: Lee Yongjoo , Sathesh‐Prabu Chandran , Kwak Geun Hwa , Bang Ina , Jung Hyun Wook , Kim Donghyuk , Lee Sung Kuk
Published: May 2021

In this study, whole‐cell biotransformation was conducted to produce nonanedioic acid from nonanoic acid by expressing the alkane hydroxylating system (AlkBGT) from Pseudomonas putida GPo1 in Escherichia coli. Following adaptive laboratory evolution, an efficient E. coli mutant strain, designated as MRE, was successfully obtained, demonstrating the fastest growth (27‐fold higher) on nonanoic acid as the sole carbon source compared to the wild‐type strain. Additionally, the MRE strain was engineered to block nonanoic acid degradation by deleting fadE. The resulting strain exhibited a 12.8‐fold increase in nonanedioic acid production compared to the wild‐type strain. Six mutations in acrR, Pcrp, dppA, PfadD, e14, and yeaR were identified in the mutant MRE strain, which was characterized using genomic modifications and RNA‐sequencing. The acquired mutations were found to be beneficial for rapid growth and nonanedioic acid production.
Lyophilization of premixed COVID‐19 diagnostic RT‐qPCR reactions enables stable long‐term storage at elevated temperature
Authors: Hammerling Michael J. , Warfel Katherine F. , Jewett Michael C.
Published: May 2021

Reverse transcriptase‐quantitative polymerase chain reaction (RT‐qPCR) diagnostic tests for SARS‐CoV‐2 are the cornerstone of the global testing infrastructure. However, these tests require cold‐chain shipping to distribute, and the labor of skilled technicians to assemble reactions and interpret the results. Strategies to reduce shipping and labor costs at the point‐of‐care could aid in diagnostic testing scale‐up and response to the COVID‐19 outbreak, as well as in future outbreaks.

In this study we test both lab‐developed and commercial SARS‐CoV‐2 diagnostic RT‐qPCR mixes for the ability to be stabilized against elevated temperature by lyophilization. Fully assembled reactions were lyophilized and stored for up to a month at ambient or elevated temperature and were subsequently assayed for their ability to detect dilutions of synthetic SARS‐CoV‐2 RNA.

Of the mixes tested, we show that one commercial mix can maintain activity and sensitivity after storage for at least 30 days at ambient temperature after lyophilization. We also demonstrate that lyoprotectants such as disaccharides can stabilize freeze‐dried diagnostic reactions against elevated temperatures (up to 50°C) for at least 30 days.

We anticipate that the incorporation of these methods into SARS‐CoV‐2 diagnostic testing will improve testing pipelines by reducing labor at the testing facility and eliminating the need for cold‐chain shipping.
Directed evolution of unspecific peroxygenase in organic solvents
Authors: Martin‐Diaz Javier , Molina‐Espeja Patricia , Hofrichter Martin , Hollmann Frank , Alcalde Miguel
Published: May 2021

Fungal unspecific peroxygenases (UPOs) are efficient biocatalysts that insert oxygen atoms into nonactivated C–H bonds with high selectivity. Many oxyfunctionalization reactions catalyzed by UPOs are favored in organic solvents, a milieu in which their enzymatic activity is drastically reduced. Using as departure point the UPO secretion mutant from Agrocybe aegerita (PaDa‐I variant), in the current study we have improved its activity in organic solvents by directed evolution. Mutant libraries constructed by random mutagenesis and in vivo DNA shuffling were screened in the presence of increasing concentrations of organic solvents that differed both in regard to their chemical nature and polarity. In addition, a palette of neutral mutations generated by genetic drift that improved activity in organic solvents was evaluated by site directed recombination in vivo. The final UPO variant of this evolutionary campaign carried nine mutations that enhanced its activity in the presence of 30% acetonitrile (vol/vol) up to 23‐fold over PaDa‐I parental type, and it was also active and stable in aqueous acetone, methanol and dimethyl sulfoxide mixtures. These mutations, which are located at the surface of the protein and in the heme channel, seemingly helped to protect UPO from harmful effects of cosolvents by modifying interactions with surrounding residues and influencing critical loops.
Role of Catalysis in Biofuels Production Process – A Review
Authors: Rehman Ayesha , Noor Tayyaba , Hussain Arshad , Iqbal Naseem , Jahan Zaib
Published: May 2021

In the past few years, biofuels have emerged as renewable alternative to encounter global energy requirements in a greener way. Biomass is a sustainable cost‐effective natural resource with wide diversity for conversion to biofuel such as biodiesel, biogas, bio‐oil, biohydrogen, etc. via various chemical, thermal, or biochemical routes. Catalysis plays a pivotal role to convert biomass to biofuels, but conventional catalysts show a lot of short comings. To address these problems, a novel nanocatalysts approach is considered to be the most promising option. Nanocatalysts offer extremely high surface area, enhanced selectivity, better stability and catalytic activity at an atomic and molecular level in comparison to bulk catalysis. Here an insight about the limitation of traditional catalysts, the importance of nanocatalysts, various types of nanocatalysts, and their application in conversion of biomass to biofuel is given. It emphasizes the state‐of‐the‐art developments in terms of catalysis and catalytic processes that are anticipated to play a crucial role in biomass conversion to fuel are emphasized and the chemistry behind nanocatalyst design for biofuel production and reduction of inhibitory effect is highlighted.
Elastic stent recoil in coronary total occlusions: Comparison of durable‐polymer zotarolimus eluting stent and ultrathin strut bioabsorbable‐polymer sirolimus eluting stent
Authors: Improta Riccardo , Scarparo Paola , Wilschut Jeroen , Wolff Quinten , Daemen Joost , Den Dekker Wijnand K , Zijlstra Felix , Van Mieghem Nicolas M , Diletti Roberto
Published: May 2021

Objectives

To compare stent recoil (SR) of the thin‐strut durable‐polymer Zotarolimus‐eluting stent (dp‐ZES) and the ultrathin‐strut bioabsorbable‐polymer Sirolimus‐eluting stent (bp‐SES) in chronic total occlusions (CTOs) and to investigate the predictors of high SR in CTOs.

Background

Newer ultrathin drug eluting stent might be associated with lower radial force and higher elastic recoil due to the thinner strut design, possibly impacting on the rate of in‐stent restenosis and thrombosis.

Methods

Between January 2017 and November 2019, consecutive patients with CTOs undergoing percutaneous coronary intervention were evaluated. Only patients treated with dp‐ZES or bp‐SES were included and stratified accordingly. Quantitative coronary angiography analysis was used to assess absolute SR, relative SR, absolute focal SR, relative focal SR, high absolute, and high relative focal SR.

Results

A total of 128 lesions (67 treated with dp‐ZES and 61 with bp‐SES) in 123 patients were analyzed. Between bp‐SES and dp‐ZES no differences were found in absolute SR (p = .188), relative SR (p = .138), absolute focal SR (p = .069), and relative focal SR (p = .064). High absolute and high relative focal SR occurred more frequently in bp‐SES than in dp‐ZES (p = .004 and p = .015). Bp‐SES was a predictor of high absolute focal SR (Odds ratio [OR] 3.29, 95% confidence interval [CI] 1.50–7.22, p = .003]. High‐pressure postdilation and bp‐SES were predictors of high relative focal SR (OR 2.22, 95% CI 1.01–4.86, p = .047; OR 2.74, 95% CI 1.24–6.02, p = .012, respectively).

Conclusions

Both stents showed an overall low SR. However, ultra‐thin strut bp‐SES was a predictor of high absolute and high relative focal SR.
Outcomes of rotational atherectomy for severely calcified coronary lesions: A single center 5‐year experience
Authors: Gao Wei , Chen Yaolin , Yang Hongbo , Yao Kang , Ge Junbo
Published: May 2021

Objectives

The aim of this study was to investigate the influences of accumulated experience on rotational atherectomy (RA) operation regarding to in‐hospital outcomes in the drug‐eluting stent (DES) era.

Methods

Between 2015 and 2019, 540 de novo lesions with calcified coronary lesions treated by RA and DES implantation at our center were retrospectively assessed. In‐hospital major adverse cardiac events (MACE) were defined as all cause death, cardiac death, target vessel revascularization, and stroke.

Results

From 2015 to 2019, RA operations were 22, 60, 102, 157, and 199 cases, respectively. Rates of procedural complications were 4.5, 3.3, 11.8, 8.3, and 7.5%, respectively. Rates of in‐hospital MACE were 0, 0, 3.9, 2.5, and 2.0%, respectively. Compared with planned RA, bailout RA was associated with more contrast use (207.5 ± 82.8 ml vs. 189.2 ± 70.0 ml, p = .008). As for procedural complications and in‐hospital outcomes, no differences were observed between two strategies. Logistic regression revealed that hypertension was independently associated with complications (OR 5.830, 95% CI 1.382–24.591, p = .016). For MACE, independent risk factors were heart failure (OR 17.593, 95% CI 1.475–209.816, p = .023) and procedural complications (OR 127.629, 95% CI 15.135–1,076.258, p < .001).

Conclusions

Along with the rapid increase of RA use and accumulated experience, rates of complications and MACE went up first and then dropped down. Hypertension was found to be an independent risk factor of procedural complications. For in‐hospital MACE, independent risk factors were heart failure and procedural complications.
Percutaneous mechanical circulatory support from the collaborative multicenter Mechanical Unusual Support in TAVI (MUST) Registry
Authors: Orvin Katia , Perl Leor , Landes Uri , Dvir Danny , Webb John George , Stelzmüller Marie‐Elisabeth , Wisser Wilfried , Nazif Tamim Michael , George Isaac , Miura Mizuki , Taramasso Maurizio , Pilgrim Thomas , Fürholz Monika , Sinning Jan‐Malte , Nickenig Georg , Rumer Chris , Tarantini Giuseppe , Masiero Giulia , Bunc Matjas , Radsel Peter , Latib Azeem , Kargoli Faraj , Ielasi Alfonso , Medda Massimo , Nombela‐Franco Luis , Vaknin‐Assa Hana , Kornowski Ran
Published: May 2021

Objectives

To evaluate the use and outcomes of percutaneous mechanical circulatory support (pMCS) utilized during transcatheter aortic valve implantation (TAVI) from high‐volume centers.

Methods and results

Our international multicenter registry including 13 high‐volume TAVI centers with 87 patients (76.5 ± 11.8 years, 63.2% men) who underwent TAVI for severe aortic stenosis and required pMCS (75.9% VA‐ECMO, 19.5% Impella CP, 4.6% TandemHeart) during the procedure (prior to TAVI 39.1%, emergent rescue 50.6%, following TAVI 10.3%). The procedures were considered high‐risk, with 50.6% having severe left ventricular dysfunction, 24.1% biventricular dysfunction, and 32.2% severe pulmonary hypertension. In‐hospital and 1‐year mortality were 27.5% and 49.4%, respectively. Patients with prophylactic hemodynamic support had lower periprocedural mortality compared to patients with rescue insertion of pMCS (log rank = 0.013) and patients who did not undergo cardiopulmonary resuscitation during the TAVI procedure had better short and long term survival (log rank <0.001 and 0.015, respectively).

Conclusions

Given the overall survival rate and low frequency of pMCS‐related complications, our study results support the use of pMCS prophylactically or during the course of TAVI (bailout) in order to improve clinical outcomes in high‐risk procedures or in case of acute life‐threatening hemodynamic collapse.
Key Parameters for the Synthesis of Active and Selective Nanostructured 3d Metal Catalysts Starting from Coordination Compounds – Case Study: Nickel Mediated Reductive Amination
Authors: Klarner Mara , Blach Patricia , Wittkämper Haiko , de Jonge Niels , Papp Christian , Kempe Rhett
Published: May 2021

The design of nanostructured catalysts based on earth‐abundant metals that mediate important reactions efficiently, selectively and with a broad scope is highly desirable. Unfortunately, the synthesis of such catalysts is poorly understood. We report here on highly active Ni catalysts for the reductive amination of ketones by ammonia employing hydrogen as a reducing agent. The key functions of the Ni‐salen precursor complex during catalyst synthesis have been identified: (1) Ni‐salen complexes sublime during catalyst synthesis, which allows molecular dispersion of the metal precursor on the support material. (2) The salen ligand forms a nitrogen‐doped carbon shell by decomposition, which embeds and stabilizes the Ni nanoparticles on the γ‐Al2O3 support. (3) Parameters, such as flow rate of the pyrolysis gas, determine the carbon supply for the embedding process of Ni nanoparticles.
Electrochemical Cleavage of Carbon‐Chlorine Bonds in Multiply Bridge‐Chlorinated Bicyclo[1.1.1]pentane‐1,3‐dicarboxylic Acids
Authors: Kaleta Jiří , Hromadová Magdaléna , Pospíšil Lubomír
Published: May 2021

Reduction of five derivatives of bicyclo[1.1.1]pentane‐1,3‐dicarboxylic acid containing one to four chlorine substituents on methylene bridges were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Electrochemical cleavage of C−Cl bonds and the reduction of H+ provided by dissociation of COOH groups are two competing processes characterized by different time constants. A concerted mechanism of C−Cl bonds cleavage is operative. The location of LUMO orbitals changes with increasing number of chlorine substituents from COOH sites to bicyclo[1.1.1]pentane. Carboxylic groups participate in the protonation of intermediates formed by the C−Cl bond rupture. The esterification of two derivatives eliminates the self‐protonation. Esters are reduced only at very negative potentials near the end of an available potential window.
Ionic Diode and Molecular Pump Phenomena Associated with Caffeic Acid Accumulated into an Intrinsically Microporous Polyamine (PIM‐EA‐TB)
Authors: Li Zhongkai , Wang Lina , Malpass‐Evans Richard , Carta Mariolino , McKeown Neil B. , Mathwig Klaus , Fletcher Philip J. , Marken Frank
Published: May 2021

The polymer of intrinsic microporosity PIM‐EA‐TB provides a molecularly rigid micropore structure containing tertiary amine sites and is shown here to interact with hydrogen bonding guest molecules such as caffeic acid. Voltammetric data with a PIM‐EA‐TB film on glassy carbon electrodes show that in both acidic solution (pH 2; PIM‐EA‐TB is protonated) and in neutral solution (pH 6; PIM‐EA‐TB is not protonated) caffeic acid is slowly accumulated into the microporous host. Binding constants are estimated and suggested to be linked to hydrogen bonding causing accumulation of caffeic acid. When employing PIM‐EA‐TB as an asymmetric membrane coated onto a 5 μm thick Teflon support film with 10 μm diameter microholes (using either a single microhole or a 10×10 array of microholes), binding of caffeic acid is shown to cause a modulation of the ionic current without affecting the pH‐dependent ionic diode behaviour. Two complementary types of effects of caffeic acid guests are discussed based on blocking anion diffusion pathways and based on removal of positive charges. The caffeic acid transport mechanism/efficiency is investigated in view of selective molecular pumping.
Rational Design of a ZIF‐67/Cobalt‐Glycolate Heterostructure with Improved Conductivity for High Cycling Stability and High‐Capacity Lithium Storage
Authors: Song Juanjuan , He Bin , Shen Honglong , Wu Zongdeng , Yu Jia , Lei Wu , Xia Xifeng , Du Ping , Hao Qingli
Published: May 2021

Cobalt‐glycolate (Co‐glycolate) is a kind of layered coordination polymer with abundant electrochemically active sites but low conductivity. The fabrication of heterostructures is a novel strategy to enhance the electrical conductivity. Herein, Co‐glycolate serves as a host substrate for the in situ growth of guest ZIF‐67 to build MOFs‐on‐CPs heterostructures (named Co‐glycolate /ZIF‐67) via a simple ligand‐exchange method as an anode for lithium‐ion batteries. A heterojunction interface with distorted lattice between the Co‐glycolate phase and the ZIF‐67 phase can be observed. Theoretical calculations and experimental results simultaneously prove that the formed heterojunction reduces the band gap and enhances the conductivity. Compared with both single components, optimized Co‐glycolate/ZIF‐67 shows a higher capacity and better cycling and rate performances due to the improved charge‐transfer rate of the heterostructure. Its specific capacity remains at 652 mAh g−1 after 800 cycles at 1 A g−1. These excellent electrochemical properties can be due to the smaller size, rough surface, and strong combination of a unique heterostructure as well as to the greatly reduced band gap of the individual components. A lithium‐storage mechanism for Co‐glycolate/ZIF‐67 was proposed. This work provides a new strategy for building MOFs‐on‐CPs heterostructures to improve the electrochemical performance of metal‐glycolate‐based electrode materials for energy‐storage and conversion systems.
The critical role of inorganic nanofillers in solid polymer composite electrolyte for Li+ transportation
Authors: Shen Zhichuan , Cheng Yifeng , Sun Shuhui , Ke Xi , Liu Liying , Shi Zhicong
Published: May 2021

Compared with commercial lithium batteries with liquid electrolytes, all‐solid‐state lithium batteries (ASSLBs) possess the advantages of higher safety, better electrochemical stability, higher energy density, and longer cycle life; therefore, ASSLBs have been identified as promising candidates for next‐generation safe and stable high‐energy‐storage devices. The design and fabrication of solid‐state electrolytes (SSEs) are vital for the future commercialization of ASSLBs. Among various SSEs, solid polymer composite electrolytes (SPCEs) consisting of inorganic nanofillers and polymer matrix have shown great application prospects in the practice of ASSLBs. The incorporation of inorganic nanofillers into the polymer matrix has been considered as a crucial method to achieve high ionic conductivity for SPCE. In this review, the mechanisms of Li+ transport variation caused by incorporating inorganic nanofillers into the polymer matrix are discussed in detail. On the basis of the recent progress, the respective contributions of polymer chains, passive ceramic nanofillers, and active ceramic nanofillers in affecting the Li+ transport process of SPCE are reviewed systematically. The inherent relationship between the morphological characteristics of inorganic nanofillers and the ionic conductivity of the resultant SPCE is discussed. Finally, the challenges and future perspectives for developing high‐performance SPCE are put forward. This review aims to provide possible strategies for the further improvement of ionic conductivity in inorganic nanoscale filler‐reinforced SPCE and highlight their inspiration for future research directions.
Study of Ground State Interactions of Enantiopure Chiral Quaternary Ammonium Salts and Amides, Nitroalkanes, Nitroalkenes, Esters, Heterocycles, Ketones and Fluoroamides
Authors: Bencivenni Grazia , Salazar Illera Diana , Moccia Maria , Houk K. N. , Izzo Joseph A. , Novacek Johanna , Grieco Paolo , Vetticatt Mathew J. , Waser Mario , Adamo Mauro F. A.
Published: May 2021

Chiral phase‐transfer catalysis provides high level of enantiocontrol, however no experimental data showed the interaction of catalysts and substrates. 1H NMR titration was carried out on Cinchona and Maruoka ammonium bromides vs. nitro, carbonyl, heterocycles, and N−F containing compounds. It was found that neutral organic species and quaternary ammonium salts interacted via an ensemble of catalyst +N−C−H and (sp2)C−H, specific for each substrate studied. The correspondent BArF salts interacted with carbonyls via a diverse set of +N−C−H and (sp2)C−H compared to bromides. This data suggests that BArF ammonium salts may display a different enantioselectivity profile. Although not providing quantitative data for the affinity constants, the data reported proofs that chiral ammonium salts coordinate with substrates, prior to transition state, through specific C−H positions in their structures, providing a new rational to rationalize the origin of enantioselectivity in their catalyses.
Positive basophil activation test with soymilk protein identifies Gly m 4–related soymilk allergy
Authors: Yoshida Tokiko , Chinuki Yuko , Matsuki Shingo , Morita Eishin
Published: May 2021

Soymilk allergy is caused by cross‐reaction of either birch Bet v 1–specific or alder Aln g 1–specific IgE to soybean Gly m 4, which belongs to pathogenesis‐related protein‐10 (PR‐10) family. Gly m 4–specific IgE test identifies soybean allergy patients with high sensitivity. In this case study, we found that CD203c expression–based basophil activation test (CD203c‐BAT) with soymilk protein became positive in the three cases of Gly m 4–related soymilk allergy at the concentrated of 1 μg/ml, but not in the control subjects. CD203c‐BAT may possibly be useful as a diagnostic tool to identify patients with soymilk allergy.
Maximum solid concentrations of coal wastewater slurries predicted by optimized neural network based on wastewater composition data
Authors: Li Dedi , Liu Jianzhong , Chen Cong , Liu He , Lv Hanjing , Cheng Jun
Published: May 2021

A variety of wastewaters can be generated in the coal chemical industry, and their treatment processes are complicated and have difficulty meeting standards. Using wastewater to prepare coal water slurry is an efficient and convenient new approach. The concentration of coal wastewater slurry is related to the content of the main wastewater components. A backpropagation neural network is developed to predict the maximum slurry concentration and analyze the mechanism at the data level according to the main component indicators, and a particle swarm algorithm is used to improve the neural network. The results are as follows: (a) it is feasible to predict the maximum concentration of coal wastewater slurry by a neural network, and a particle swarm algorithm can effectively improve the prediction accuracy in different models, reducing mean absolute error by up to 0.44%; (b) different input factors have different impacts on model prediction results—organic matter, ammonia nitrogen, and monovalent metal ions content as input factors to predict the maximum slurry concentration can get the most accurate results, obtaining a mean absolute error of 0.16% for the optimized backpropagation neural network and the lowest mean square error; and (c) divalent metal ions and phenols content are not suitable as input factors for predicting, as they all cause an increase in model error due to their weak or complex effects on the slurryability.
Rh(III)‐Catalyzed Diverse C—H Functionalization of Iminopyridinium Ylides
Authors: Dong Zhenzhen , Li Pengfei , Li Xingwei , Liu Bingxian
Published: May 2021

Main observation and conclusion

Divergent synthesis of useful skeletons has been realized via rhodium(III)‐catalyzed C—H activation of iminopyridinium ylides and coupling with various unsaturated coupling reagents. Isocoumarins and isoquinolones were obtained via cleavage of the C—N or N—N bond in the ylidic directing group, while fluorinated alkenes were delivered with the directing group intact. The reactions occurred with wide substrate scopes and good efficiency under redox‐neutral and air‐tolerant conditions. Representative products exhibit solid‐state fluorescent property and bioactivity of inhibition toward human cancer cells.
Enantioselective Resolution Copolymerization of Racemic 2,3‐Disubstituted cis‐Epoxides with CO2 Mediated by Binuclear Cobalt(III) Catalyst†
Authors: Liu Yan‐Lan , He Guang‐Hui , Liu Ye , Lu Xiao‐Bing
Published: May 2021

Main observation and conclusion

Enantioselective resolution copolymerization of racemic internal epoxides with carbon dioxide (CO2) is a challenging issue because of their poor reactivity and complicated regio/stereoselectivity. Herein, we describe the first enantioselective resolution copolymerization of racemic aromatic 2,3‐disubstituted cis‐epoxides and CO2 using enantiopure dinuclear cobalt(III) complexes as catalyst under mild conditions, affording the corresponding polycarbonates with completely alternating structure and good enantioselectivity in the range of 70% to 97% ee. The isotactic polycarbonate from β‐methylstyrene oxide is a typical semicrystalline material, possessing a melting point of 241 oC; while other isotactic‐enriched copolymers from 2,3‐disubstituted cis‐epoxides bearing a substitute group on the aromatic ring are amorphous, having glass transition temperatures between 86 oC and 124 oC. Interestingly, the copolymer selectivity is correlated well with the Hammett substituent constant, and the highest polymer selectivity of 98% was found in the system using the epoxides bearing an electron‐donating group on the benzene ring.
High Tg Polymer Insulator Yields Organic Photovoltaic Blends with Superior Thermal Stability at 150 oC
Authors: Chen Fei , Zhang Ying , Wang Qi , Gao Mengyuan , Kirby Nigel , Peng Zhongxiang , Deng Yunfeng , Li Miaomiao , Ye Long
Published: May 2021

Main observation and conclusion

Record‐breaking organic solar cells (OSCs) based on blends of polymer donors and small molecule acceptors often show undesirable degradation, which severely precludes their practical use. Herein, we demonstrate a facile and cost‐effective approach to construct thermally stable OSCs at 150 oC by incorporating a small amount of a polymer insulator polyacenaphthylene (PAC) with high glass‐transition temperature over 230 oC into polymer:acceptor blends. The model PTB7‐Th:EH‐IDTBR blend with 10 wt% PAC maintained above 85% of its initial efficiency upon continuous heating at 150 oC for over 800 h, while the efficiency of the blend without PAC sharply dropped by 70% after ~300 h. Owing to high miscibility with acceptors, PAC confines the motion of the acceptor molecules and suppresses the acceptor crystallization at elevated temperatures, leading to significantly improved stability. Importantly, the effectiveness of this blending approach was also validated in many other OSC systems, showing great potential for achieving high‐performance thermally stable electronics.
Structural Basis of RACK7 PHD Domain to Read a Pediatric Glioblastoma‐Associated Histone Mutation H3.3G34R
Authors: Lan Wenxian , Li Ze , Jiao Fangfang , Wang Chunxi , Guo Rui , Cao Chunyang
Published: May 2021

Main observation and conclusion

Histone point mutations, including missense mutations on histone H3 at positions 27 (K27M), 34 (G34R/V, G34W, G34L) and 36 (K36M), were identified as potential cancer driver mutations. H3.3G34R/V mutations account for pediatric glioblastomas (GBM). RACK7 (also known as ZMYND8, PRKCBP1) was recently reported to specifically bind H3.3G34R through its PHD (plant homedomain) domain (PHDRACK7) in vitro and in H3.3G34R pediatric glioblastoma cells, playing key roles in H3.3G34R‐mediated gene transcription. Herein, we provided both biochemical and NMR structural evidences that PHDRACK7 recognized histone H3.3G34R mutant via a mechanism distinct from all other reported PHD domains. Except the reported residue D104, two new sites D108 and L121 of PHDRACK7 were found necessary for the interactions between PHDRACK7 and histone H3.3G34R peptide. Our results provided a potential molecular basis for pediatric GBM driven by the H3.3G34R mutation.
Mode of death in elderly and super‐elderly patients with acute heart failure: Insights from Japanese heart failure registry
Authors: Takabayashi Kensuke , Kitaguchi Shouji , Yamamoto Takashi , Takenaka Kotoe , Takenaka Hiroyuki , Fujita Ryoko , Okuda Miyuki , Nakajima Osamu , Koito Hitoshi , Terasaki Yuka , Kitamura Tetsuhisa , Nohara Ryuji
Published: May 2021

Background

In Japan, both the prevalence of the elderly and super‐elderly and those of acute heart failure (AHF) have been increasing rapidly.

Methods

This registry was a prospective multicenter cohort, which enrolled a total of 1253 patients with AHF. In this study, 1117 patients' follow‐up data were available and were categorized into three groups according to age: <75 years old (nonelderly), 75–84 years old (elderly), and ≥ 85 years old (super‐elderly). The endpoint was defined as all‐cause death and each mode of death after discharge during the 3‐years follow‐up period.

Results

Based on the Kaplan–Meier analysis, a gradually increased risk of all‐cause death according to age was found. Among the three groups, the proportion of HF death was of similar trend; however, the proportion of infection death was higher in elderly and super‐elderly patients. After adjusting for potentially confounding effects using the Cox and Fine–Gray model, the hazard ratio (HR) of all‐cause death increased significantly in elderly and super‐elderly patients (HR, 2.60; 95% confidence interval [CI], 1.93–3.54 and HR, 5.04; 95% CI, 3.72–6.92, respectively), when compared with nonelderly patients. The highest sub‐distribution HR in detailed mode of death was infection death in elderly and super‐elderly patients (HR, 4.25; 95% CI, 1.75–10.33 and HR, 10.10; 95% CI, 3.78–27.03, respectively).

Conclusions

In this population, the risk of all‐cause death was found to increase in elderly and super‐elderly. Elderly patients and especially super‐elderly patients with AHF were at a higher risk for noncardiovascular death, especially infection death.
Functional link convolutional neural network for the classification of diabetes mellitus
Authors: Jangir Sunil Kumar , Joshi Nakul , Kumar Manish , Choubey Dilip Kumar , Singh Shatakshi , Verma Madhushi
Published: May 2021

Diabetes is a faction of metabolic ailments distinguished by hyperglycemia which is the consequence of a defect, in the action of insulin, insulin secretion, or both and producing various abnormalities in the human body. In recent years, the utilization of intelligent systems has been expanded in disease classification and numerous researches have been proposed. In this research article, a variant of Convolutional Neural Network (CNN) that is, Functional Link Convolutional Neural Network (FLCNN) is proposed for the diabetes classification. The main goal of this article is to find the potential of a computationally less complex deep learning network like FLCNN and applied the proposed technique on a real dataset of diabetes for classification. This article also presents the comparative studies where various other machine learning techniques are implemented and outcomes are compared with the proposed FLCNN network. The performance of each classification techniques have been evaluated based on standard measures and also validated with a non‐parametric statistical test such as Friedman. Data for modeling diabetes classification is collected from Bombay Medical Hall, Upper Bazar, Ranchi, India. Accuracy achieve by the proposed classifier is more than 90% which is closer to the other state‐of‐the‐art implemented classifiers.
Pediatric Pleomorphic Xanthoastrocytoma: A National Database Inquiry on Current Treatment Approaches in the United States
Authors: Scarpelli Daphne B. , Yu Yun , Tep Amanda C. , Bergue Bailey , Degnin Catherine , Chen Yiyi , McClelland Shearwood , Jaboin Jerry J.
Published: May 2021

Background

Pleomorphic xanthoastrocytomas (PXAs) account for <1% of primary brain tumors, occurring predominantly in children and young adults. Surgical resection serves as the primary treatment for PXAs, while radiotherapy (RT) and chemotherapy protocols remain poorly defined.

Aim

This study aims to determine current care patterns utilized for pediatric patients (≤ 18 years) diagnosed with PXAs and their effect on overall survival.

Methods

The United States National Cancer Database (NCDB) was queried between 2004 and 2015 for pediatric patients (≤18 years) diagnosed with PXAs.

Results

From the 224 qualifying patients, most patients proceeded with surgery only (78.1%), while 11.6% of patients received both adjuvant RT and chemotherapy. In the 2010‐2015 cohort, patients with subtotal resection were associated with poorer prognosis than those with gross‐total resection (hazard ratio = 17.44, 95% confidence interval = 2.10‐144.90, p < .001). RT and chemotherapy recipients were similarly associated with poorer survival than those treated with surgery only, with p‐values of <.001 and respective hazard ratios of 3.82 (95% confidence interval = 1.85‐7.90) and 6.68 (95% confidence interval = 3.21‐13.89). The key factors impacting the probability of RT delivery involved WHO grade (p < .001) and chemotherapy administration (p < .001). However, WHO grade alone did not significantly impact survival (p‐value = .088).

Conclusion

Maximally safe resection is the current treatment goal for patients with PXAs. RT and chemotherapy are poorly utilized but had a greater role in managing more aggressive cases of PXAs. Additional research focusing on the impact of adjuvant therapies on tumor progression is needed to better guide treatment decisions.