bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Electronic Structure and Bonding in Endohedral Actinidofullerenes
Authors: Rodriguez-Fortea Antonio , Morales-Martinez Roser , Moreno-Vicente Antonio , Dunk Paul W. , Chen Ning , Echegoyen Luis , Poblet Josep M.
Published: May 2020

Endohedral metallofullerenes (EMF), i.e. fullerenes that contain metal atoms or metal clusters in their inner void space, have been intensively studied since the isolation of La@C82.1 In 1999, the synthesis and characterization of the first clusterfullerene Sc3N@C80 using the Krätschmer-Huffman method was a milestone in the field of EMF.2 Since this pioneering work, many EMF have been obtained and characterized,3 among them actinide endofullerenes,4 as for example the dimetallic U2@C80.5 In this compound, the metal-metal distance from X-ray diffraction was found to be ranged between 3.46 and 3.79 Å, quite a long bond distance to suppose the presence of a strong metal-metal bond, as observed previously for dimetallic (lanthanide)2@C2n. This experimental confirmation of a weak U-U bonding interaction in a molecular structure is certainly very encouraging, but we were wondering whether it is possible to isolate a compound with a strong U-U bond or not. In this communication we analyze the characteristic electronic structure of a family of endohedral actinidofullerenes related to U2@C80 and discuss about the challenging task of synthesizing new systems showing strong actinide-actinide interaction in the confined space of a fullerene.

References

1. Chai, Y.; Cuo, T.; Jin, C.; Haufler, R. E.; Felipe Chibante, L. P.; Fure, J.; Wang, L.; Alford, J. M.; Smalley, R. E. J. Phys. Chem.
1991, 95, 7564-7568.

2. Stevenson, S.; Rice, G.; Glass, T.; Harich, K.; Cromer, F.; Jordan, M. R.; Craft, J.; Hadju, E.; Bible, R.; Olmstead, M. M.; Maitra, K.; Fisher, A. J.; Balch, A. L.; Dorn, H. C., Nature
1999,
401, 55.

3. Popov, A. A.; Yang, S.; Dunsch, L. Chem. Rev.
2013,
113, 5989-6113.

4. a) Wang, Y.; Morales-Martínez, R. et al.J. Am. Chem. Soc.,
2017, 139, 5110-5116; b) Cai, W. C.; Morales-Martínez, R. et al. Chem. Sci.
2017, 8, 5282-5290; c) Cai, W.; Abella, L. et al.J. Am. Chem. Soc.,
2018, 140, 18039-18050.

5. Zhang, X.; Wang, Y.; Morales-Martínez, R.; Zhong, J.; de Graaf, C.; Rodríguez-Fortea, A.; Poblet, J. M.; Echegoyen, L.; Feng, L.; Chen, N. J. Am. Chem. Soc.,
2018, 140, 3907-3915.
(Invited) Synthesis and Properties of Endohedral Open-Cage Fullerenes
Authors: Murata Yasujiro
Published: May 2020

Open-cage fullerene derivatives are fascinating molecules because a small molecule can be introduced inside the fullerene cage through the opening. When the NMR active molecules are introduced inside the open-cage fullerene derivatives, the resulting endohedral species are used for the study with the encapsulated molecule as a magnetic probe.

First, the regioselectivity in the Diels.Alder reaction of an unsymmetrical open-cage C60 derivative with anthracene was studied. By using an encapsulated H2 molecule as a magnetic probe, the product population was successfully evaluated in detail, indicating the formation of approximately ten compounds as major components. The NICS calculations showed a close resemblance to the observed 1H NMR spectrum, which allowed for a facile characterization of the products. Theoretical studies on the formation of all 29 possible anthracene adducts were also performed. The results indicated that the regioselectivity is strongly governed by steric factors, values of the frontier orbital coefficients, and thermodynamic stabilities. Single-crystal X-ray analysis of the dominant compound revealed the supramolecular architecture between the anthracene moiety and the Π-sphere of a neighboring molecule.[1]

Second, The H2O/CH2=CH2-type hydrogen-bonding model was experimentally constructed using a water complex of an open-cage C60 derivative, in which an olefinic double bond and a single molecule of H2O are geometrically confined. To investigate OH/Π-type H-bonding, we performed 1H NMR spectroscopic studies that demonstrated the monotonic downfield shift of the proton signal corresponding to H2O with remarkable rotational perturbation by lowering the temperature. From the temperature dependence of the angular momentum correlation time, the interaction energy was quantitatively estimated to be ca. 0.3 kcal/mol. The computational studies were thoroughly conducted to clarify its inherent nature. As a consequence, the orientation of H2O was found to play a prominent role in varying the bonding strength as well as contribution from the electrostatic attraction and orbital-orbital interaction significantly driven by the favorable orbital overlap.[2]

[1] Probing the Regioselectivity by Encapsulated H2: Diels-Alder Reaction of a Cage-Opened C60 Derivative with Anthracene, Hashikawa, Y.; Murata, Y. Chem. Eur. J. 2019, 25, 2482-2485.

[2] H2O/Olefinic-Π Interaction inside a Carbon Nanocage, Hashikawa, Y.; Murata, Y. J. Am. Chem. Soc. 2019, 141, 12928-12938.
(Invited) Creation of High-Performance Perovskite Solar Cells Using Lithium Ion Endohedral Fullerenes
Authors: Matsuo Yutaka
Published: May 2020

It was started to be realized that lithium-ion endohedral fullerenes are useful materials for electronic devices as shown by Li+@C60 enhancing performance in perovskite solar cells.1) Li+@C60 has high electron affinity, and has oxidation ability to take an electron from organic semiconductors instantly only by mixing these materials. Hereat Li+@C60 has been expected as a p-type dopant to improve performance of organic semiconductors. On the other hand, our next target is a neutral lithium endohedral fullerene (Li@C60) as an n-type dopant for electron donation. To date, Li@C60 has been prepared through electrolysis as electrochemical reduction. This method requires us to use electrochemical instruments and elaborate technique to control current/voltage and temperature by a skillful researcher. To solve this issue, we investigated the synthesis of Li@C60 by facile and scalable chemical reduction of Li+@C60.2)

Treatment of Li+@C60 with decamethylferrocene as a commercially available mild chemical reductant afforded the neutral Li@C60 in 81% isolated yield. The product exists as mainly dimer form in solid state containing minute amount the monomer form, which part is ESR active. XRD, ESR, and Raman spectroscopic measurements revealed characteristics of this solid. In this talk, we will introduce fabrication and performance of organic thin-film devices involving Li+@C60 and/or Li@C60.1) It was found that Li@C60, which was derived from Li+@C60 with accepting an electron from organic semiconducting molecules, scavenged intruding oxygen molecules into the devices to improve the lifetime of the organic semiconducting devices.3,4)

【References】

1) I. Jeon, H. Ueno, S. Seo, K. Aitola, R. Nishikubo, A. Saeki, H. Okada, G. Boschloo, S. Maruyama, Y. Matsuo, Angew. Chem. Int. Ed. 2018, 57, 4607.

2) H. Okada, H. Ueno, Y. Takabayashi, T. Nakagawa, M. Vrankić, J. Arvanitidis, T. Kusamoto, K. Prassides, Y. Matsuo, Carbon
2019, 53, 467.

3) H. Ueno, I. Jeon, H.-S. Lin, A. Thote, T. Nakagawa, H. Okada, S. Izawa, M. Hiramoto, H. Daiguji, S. Maruyama, Y. Matsuo, Chem. Commun.
2019, 55, 11837

4) I. Jeon, A. Shawky, H.-S. Lin, S. Seo, H. Okada, J.-W. Lee, A. Pal, S. Tan, A. Anisimov, E. I. Kauppinen, Y. Yang, S. Manzhos, S. Maruyama, Y. Matsuo, J. Am. Chem. Soc.
2019, 141, 16553.
(Invited) Preparation of Open-Cage Fullerene Derivatives By Rhodium(I)-Catalyzed [2+2+2] Cycloaddition of Diynes and C60: Synthesis, Computational Studies and Application in Perovskite Solar Cells
Authors: Artigas Albert , Castro Edison , Pla-Quintana Anna , Echegoyen Luis , Lledó Agustí , Roglans Anna , Solà Miquel
Published: May 2020

Since the discovery of C60 in 1985 [1], fullerenes have attracted the attention of chemists due to their unique structure, properties and reactivity, along with their potential applications in a variety of fields ranging from materials science to biomedicine [2–3]. The preparation of cyclohexadiene-fused C60 derivatives can be achieved by [2+2+2] cycloaddition reactions of C60 with alkynes [4–6]. This particular class of fullerene derivatives is interesting from the synthetic point of view because they can be converted into the corresponding open-cage bis(fulleroids) when subjected to photochemical conditions [7]. Based on our previous theoretical DFT study that showed the viability of a rhodium-catalyzed [2+2+2] cycloaddition reaction of two alkynes and C60 [8], here we report the first example of [2+2+2] cycloaddition involving C60 and diynes under catalytic conditions promoted by a rhodium(I) catalyst, which leads to the formation of a series of bis(fulleroids) [9]. The process takes place in a single step and no photoexcitation is required. The process mechanism has been studied by means of DFT calculations, proving that the cyclohexadiene-fused intermediate resulting from a [2+2+2] cycloaddition evolves into the final product through a Rh-catalyzed di-π-methane rearrangement. Finally, the electrochemical behavior of the synthesized products has also been studied, as well as their performance as electron transporting materials (ETMs) in perovskite solar cells (PSCs) [10].

References:

[1] Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. Nature
1985, 318, 162.

[2] Langa, F.; Nierengarten, J. F. Fullerenes: principles and applications. 1st ed., Royal Society of Chemistry, Cambridge, 2011.

[3] Castro, E.; Garcia, A. H.; Zavala, G.; Echegoyen, L. J. Mater.
Chem. B.
2017, 5, 6523.

[4] Hsiao, T.-Y.; Santhosh, K. C.; Liou, K.-F.; Cheng, C.-H J. Am. Chem Soc.
1998, 120, 12232.

[5] Liou, K.-F.; Cheng, C.-H. J.
Chem. Soc. Chem. Commun. 1995, 1603.

[6] Inoue, H.; Yamaguchi, H.; Suzuki, T.; Akasaka, T.; Murata, S. Synlett
2000, 1178.

[7] Vougioukalakis, G. C.; Roubelakis, M. M.; Orfanopoulos, M. Chem. Soc. Rev. 2010, 39, 817.

[8] Artigas, A.; Lledó, A.; Pla-Quintana, A.; Roglans, A.; Solà, M. Chem. Eur. J.
2017, 23, 15067.

[9] Artigas, A.; Lledó, A.; Pla-Quintana, A.; Roglans, A.; Solà, M. Chem. Eur. J.
2018, 24, 10653.

[10] Castro, E.; Artigas, A.; Pla-Quintana, A.; Roglans, A.; Liu, F.; Perez, F.; Lledó, A.; Zhu, X.-Y.; Echegoyen, L. Materials
2019, 12, 1314.

Figure 1
(Invited) Donor-Acceptor Systems from Triplet Photosensitizers for High Potential, Long-Lived Charge Separation
Authors: Shao Shuai , D'Souza Francis , Obondi Christopher , Subedi Diliraj , Lim Gary N. , Gobeze Haptom B. , Karr Paul , Poddutoori Prashanth K , van der Est Art
Published: May 2020

Generation of high potential, long-lived charge separated states in donor-acceptor systems are invaluable for converting light energy into either electricity or fuels. The majority of the donor-acceptor conjugates designed for this purpose are derived mainly from short-lived singlet sensitizers.1,2 In such conjugates, charge separation from the singlet excited donor or acceptor results in a short-lived charge separated state of singlet spin character. Alternatively, by utilizing high-energy triplet sensitizers one could generate long-lived charge separated states. The radical ion-pairs of triplet spin character slowly charge recombine to the ground state due to spin forbidden process. However, witnessing such a process purely from the triplet-excited state without the interference of the singlet excited state and other competing photochemical events such as excitation energy transfer has been challenging to establish.3-5

Here, we summarize our efforts to synthesize donor-acceptor conjugates bearing triplet sensitizers wherein excited state electron transfer exclusively occurs from the triplet excited state.3-6 To achieve the goal, two types of triplet sensitizers, viz., palladium and platinum porphyrins, and b-iodo functionalized BODIPYs are covalently linked to the well-known electron acceptor, fullerene, C60. Using femtosecond transient absorption studies covering wide temporal and spatial regions, and time-resolved electron paramagnetic studies, photoinduced electron transfer from 3MP* (M = Pd or Pt) to C60 in these dyads, leading to the formation of MP•+-C60
•- charge separated state of triplet spin character is demonstrated. Similarly, the role of triplet sensitizers in promoting charge separation in I2BODIPY-C60 and I2azaBODIPY-C60 dyads6 is also highlighted.

1. B. KC, F. D’Souza, Coord. Chem. Rev. 2016, 322, 104-141.

2. D’Souza, and O. Ito ‘Chem. Soc. Rev. 2012,
41, 86-96.

3. Obondi, G. N. Lim, F. D’Souza, J. Phys. Chem. C 2015, 119, 176-185.

4. Obondi, G. N. Lim, B. Churchill, P. K. Poddutoori, A. van der Est, and F. D’Souza, Nanoscale, 2016, 8, 8333-8344.

5. K. Poddutoori,Y. E. Kandrashkin, C. O. Obondi, F. D’Souza and A. van der Est, Phys. Chem. Chem. Phys. 2018, 20, 28223-28231.

6. Shao, H. B. Gobeze, V. Bandi, C. Funk, B. Heine, M. J. Duffy, V. Nesterov, P. A. Karr, F. D’Souza, ChemPhotoChem, 2020, in press.
(Invited) Isolation and Structure Determination of Trifluoromethylated Gadoliniummetallofullerenes
Authors: Aoyagi Shinobu , Nakagawa Ayano , Omachi Haruka , Shinohara Hisanori
Published: May 2020

Endohedral metallofullerenes have been extensively studied since the first experimental observation of La@C60 in a laser-vaporized supersonic beam in 1985. However, most of these studies have focused on metallofullerenes larger than C60 such as Ln@C82 (Ln: lanthanide). There are few examples for isolation of small-cage (C60, C70, C72, and C74) lanthanide metallofullerenes because of their extremely high chemical reactivity. Recently, we developed an in situ trifluoromethylation method for the extraction and purification of these missing metallofullerenes [1−3]. Here we report the isolation and structure determination of trifluoromethylated gadolinium metallofullerenes (Gd@C60(CF3)3, Gd@C60(CF3)5, Gd@C70(CF3)3, Gd@C74(CF3), and Gd@C74(CF3)3). Gd-metallofullerenes are promising as magnetic resonance imaging (MRI) contrast agents. The fully enclosing carbon cage completely prevents leaching of the Gd atoms, resulting in lower toxicity than commercially available metal chelate reagents such as Gd-DTPA.

Trifluoromethylated Gd-metallofullerenes were synthesized by the modified arc-discharge method. PTFE rods are placed near the discharge area as CF3 source. During arc discharge, PTFE was decomposed and evaporated to produce CF3 radicals. Gd-metallofullerenes and empty fullerenes were extracted from the raw soot with o-xylene. Rapid separation of Gd-metallofullerenes from empty fullerenes was carried out by the TiCl4 Lewis acid method. High-performance liquid chromatography (HPLC) purification was conducted for isolation of trifluoromethylated Gd-metallofullerenes. Single crystals of trifluoromethylated Gd-metallofullerenes were obtained from solution. The single-crystal X-ray diffraction data for structure determination were collected at SPring-8 large synchrotron radiation facility.

Figures show the molecular structures of Gd@C74(CF3) (I), Gd@C74(CF3) (II), and Gd@C74(CF3)3 derived from the X-ray crystal structure analysis. The closed-shell molecular structures are theoretically stable and have wide HOMO-LUMO energy gaps.

[1] Z. Wang et al. Angew. Chem. Int. Ed. 55, 199 (2016).

[2] A. Nakagawa et al. Nature. Commun. 9, 3073 (2018).

[3] A. Nakagawa et al. R. Soc. Open Sci. 5, 181015 (2018).

Figure 1
(Invited) Isomerism in Endohedral Fullerenes: Isomeric Cages, Isomeric Encapsulates
Authors: Uhlik Filip , Slanina Zdenek , Adamowicz Ludwik , Akasaka Takeshi , Lu Xing
Published: May 2020

Computations can help understanding of various forms of isomerism in endohedral fullerenes. They can confirm the observed isomers, predict their abundancies and properties, deduce approximate temperature during synthesis (or other parameters difficult to measure) from observed isomeric ratios. These features will be illustrated on topical isomeric systems like Ce@C82, Eu@C86, C86, (H2O)3@C84, nanoelectronic devices based on fullerenes and others. Factors influencing comparison of experiments and calculations will be also discussed like kinetics, catalysis, solubility, metal sources, effects of the crystal environment.
(Invited) Reactivity of Li+@C60@C240 and Photoinduced Charge Shift in Li+ Doped Giant Nested Fullerenes
Authors: Solà Miquel , Luque-Urrutia Jesús Antonio , Stasyuk Antony J. , Stasyuk Olga A. , Poater Albert , Voityuk Alexander A.
Published: May 2020

Over the last years, carbon nano-onions (CNOs) have been in focus in material science research. Apart from its prospective use in solar cells, the number of potential applications of CNOs have grown in the last decades. Among them, we can mention their application in gas storage processes, solid lubrication, or heterogeneous catalysis, and also as electrode materials in capacitors, anode materials in lithium-ion batteries, catalyst support in fuel cells, or electro-optical devices. From the analysis of the polarizability of CNOs, it was concluded that CNOs behave as near perfect nanoscopic Faraday cages.[1] If CNOs behave as ideal Faraday cages, the reactivity of the C240 cage should be the same in Li+@C240 and Li+@C60@C240. In the first part of this work, we have analyzed the Diels-Alder reaction of cyclopentadiene to the free C240 cage and the C60@C240 CNO together with their Li+-doped counterparts using density functional theory. We find that in all cases the preferred cycloaddition is on bond [6,6] of type B of the C240 cage. From the comparison between the reactivity of Li+@C240 and Li+@C60@C240, we conclude that C60@C240 does not act as a perfect Faraday cage.[2] In the second part of this work, we perform a systematic study of excited state properties of six double-layered Li+ doped fullerenes of Ih

symmetry: [Li@C60@C240]+, [Li@C60@C540]+, [Li@C60@C960]+, [Li@C240@C540]+, [Li@C240@C960]+ and [Li@C540@C960]+. On the basis of TDDFT calculations, we show that the long-wave absorption by the Li+ doped species leads to charge transfer (CT) between the inner and the outer shells unlike their neutral double-layered precursors. The CT energy depends strongly on the size of the concentric fullerenes and it can easily be tuned by varying both the encapsulated metal ion and the size of the shells. Two types of low-lying excited states are identified (1) capacitor-like structures, as Li+@C60
-@C240
+, with alternating positive and negative charges, and (2) states, where the positive charge is delocalized over the outer shell, as in Li@C240@C540
+.[3]

References

[1] R. R. Zope, J. Phys. B: At. Mol. Opt. Phys. 41 (2008) 41, 085101; [b] R. R. Zope, S. Bhusal, L. Basurto, T. Baruah and K. Jackson, J. Chem. Phys. 143 (2015) 084306.

[2] A. J. Luque-Urrutia, A. Poater and M. Solà. Submitted for publication.

[3] A. J. Stasyuk, O. A. Stasyuk, M. Solà and A. A. Voityuk. J. Phys. Chem. C 123 (2019) 16525-16532.

Figure 1
(Invited) Excited States of Atoms Encapsulated in the C60 Cage: A Spin-Polarized Time-Dependent Density-Functional Study
Authors: Saito Susumu , Torii Haruki , Toyoda Masayuki , Wakabayashi Tomonori , Kanai Yasuyuki , Sasao Noboru , Yoshimura Motohiko
Published: May 2020

Among various endohedral fullerenes, "X@C60", the icosahedral-symmetry C60 cage and an atom trapped inside the cage, has been studied for more than thirty years ever since the proposal of the C60 fullerene cage based on the carbon-cluster mass spectra because of its importance from the viewpoint of an artificial atom and also as the realization of an isolated singel atom trapped inside the chemically inert cage. The system is now also attracting interests in the field of neutrino mass spectroscopy for using the coherent isolated atoms to detect the radiative emission of neutrino pair. In the present work, we study the excited state properties of atoms trapped inside the C60 cage using the spin-ploarized time-dependent density-functional theory. In the Figure, the photoabsorption spectra of the empty C60 cage, the N atom, and the N@C60 system are shown. From the spin-polarization analysis, the peak at 8.5 eV of the N@C60 spectrum is found to correspond to the excitation of the N atom trapped inside the C60 cage. The presence of the outer C60 cage therefore slightly modifies the excitation energy of the N atom by +0.2 eV. We will also discuss the excitations of various atoms including Cu, Ag, and Au atoms which are trapped inside the C60 cage.

Figure 1
β-Hydroxybutyrate is reduced in humans with obesity-related NAFLD and displays a dose-dependent effect on skeletal muscle mitochondrial respiration in vitro
Authors: Mey Jacob T. , Erickson Melissa L. , Axelrod Christopher L. , King William T. , Flask Chris A. , McCullough Arthur J. , Kirwan John P.
Published: May 2020

Nonalcoholic fatty liver disease (NAFLD) is characterized by hepatic fat accumulation and impaired insulin sensitivity. Reduced hepatic ketogenesis may promote these pathologies, but data are inconclusive in humans and the link between NAFLD and reduced insulin sensitivity remains obscure. We investigated individuals with obesity-related NAFLD and hypothesized that β-hydroxybutyrate (βOHB; the predominant ketone species) would be reduced and related to hepatic fat accumulation and insulin sensitivity. Furthermore, we hypothesized that ketones would impact skeletal muscle mitochondrial respiration in vitro. Hepatic fat was assessed by 1H-MRS in 22 participants in a parallel design, case control study [Control: n = 7, age 50 ± 6 yr, body mass index (BMI) 30 ± 1 kg/m2; NAFLD: n = 15, age 57 ± 3 yr, BMI 35 ± 1 kg/m2]. Plasma assessments were conducted in the fasted state. Whole body insulin sensitivity was determined by the gold-standard hyperinsulinemic-euglycemic clamp. The effect of ketone dose (0.5–5.0 mM) on mitochondrial respiration was conducted in human skeletal muscle cell culture. Fasting βOHB, a surrogate measure of hepatic ketogenesis, was reduced in NAFLD (−15.6%, P < 0.01) and correlated negatively with liver fat ( r2 = 0.21, P = 0.03) and positively with insulin sensitivity ( r2 = 0.30, P = 0.01). Skeletal muscle mitochondrial oxygen consumption increased with low-dose ketones, attributable to increases in basal respiration (135%, P < 0.05) and ATP-linked oxygen consumption (136%, P < 0.05). NAFLD pathophysiology includes impaired hepatic ketogenesis, which is associated with hepatic fat accumulation and impaired insulin sensitivity. This reduced capacity to produce ketones may be a potential link between NAFLD and NAFLD-associated reductions in whole body insulin sensitivity, whereby ketone concentrations impact skeletal muscle mitochondrial respiration.
Prediction of Horizontal Pneumatic Conveying of Large Coal Particles Using Discrete Phase Model
Authors: Yang Daolong , Li Ge , Wang Yanxiang , Wang Qingkai , Li Jianping , Huang Qianqian , Xia Youtao , Li Qian
Published: May 2020

The pneumatic conveying focusing on gas‐solid two‐phase flow plays an important role in a conveying system. Previous work has been conducted in the fields of small particles, where the size was less than 5 mm; however, there are few studies regarding large sizes (>5 mm). In order to predict the horizontal pneumatic conveying of large coal particles, the coupling methods based on the Euler–Lagrange approach and discrete phase model (DPM) have been used for the simulated research. Compared with the experimental results under the same working condition, the particle trajectory obtained by simulation is similar to the particle distribution at the same position in the experiment, and it turns out that the simulation method is feasible for the horizontal pneumatic conveying of large particles. Multifactor simulations are also carried out to analyse the effects of particle size, flow field velocity, solid‐gas rate, and pipe diameter on the wall abrasion during horizontal pneumatic conveying, which provides simulation reference and design guide for pneumatic conveying of large particles.
Role of Gas6 and TAM Receptors in the Identification of Cardiopulmonary Involvement in Systemic Sclerosis and Scleroderma Spectrum Disorders
Authors: Bellan Mattia , Dimagli Arnaldo , Piccinino Cristina , Giubertoni Ailia , Ianniello Aurora , Grimoldi Federico , Sguazzotti Maurizio , Nerviani Alessandra , Barini Michela , Carriero Alessandro , Smirne Carlo , Burlone Michela Emma , Rigamonti Cristina , Minisini Rosalba , Salmi Livia , Barbaglia Matteo Nazzareno , Castello Luigi Mario , Sola Daniele , Marino Paolo , Avanzi Gian Carlo , Pirisi Mario , Sainaghi Pier Paolo
Published: May 2020

Background. Few biomarkers are available for early identification of pulmonary arterial hypertension (PAH) and interstitial lung disease (ILD) in systemic sclerosis (SS) and scleroderma spectrum disorders (SSD). Aims. To evaluate Gas6, sAxl, and sMer as biomarkers for cardiopulmonary complications of SS and SSD. Methods. In a cross-sectional observational study, we recruited 125 consecutive patients, affected by SS and SSD and referred to a tertiary-level pulmonary hypertension outpatient clinic. All patients underwent a comprehensive evaluation for identification of PAH and ILD. Gas6, sMer, and sAxl concentrations were measured with ELISA protocols, and concentrations were compared according to PAH or ILD. Results. Nineteen subjects had pulmonary hypertension (PH) (14 PAH), and 39 had ILD (6 severe). Plasma sMer was increased in PAH (18.6 ng/ml IQR [11.7-20.3]) with respect to the absence (12.4 [8.0-15.8]) or other form of pulmonary hypertension (9.6 [7.4-12.5]; K–W variance p<0.04). Conversely, Gas6 and sAxl levels were slightly increased in mild ILD (25.8 ng/ml [19.5-32.1] and 24.6 [20.1-32.5]) and reduced in severe ILD (16.6 [15.0-22.1] and 15.5 [14.9-22.4]) in comparison to no evidence of ILD (23.4 [18.8-28.1] and 21.6 [18.1-28.4]; K–W, p≤0.05). Plasma sMer≥19 ng/ml has 50% sensitivity and 92% specificity in PAH identification (area under the ROC curve (AUC) 0.697, p<0.03). Values of Gas6≤24.5 ng/ml and of sAxl≤15.5 ng/ml have 100% and 67% sensitivity and 47% and 86% specificity, respectively, in identifying severe ILD (Gas6 AUC 0.787, p<0.001; sAxl AUC 0.705, p<0.05). Conclusions. The assay of Gas6 sAxl and sMer may be useful to help in the identification of PAH and ILD in SS and SSD patients. The Gas6/TAM system seems to be relevant in cardiopulmonary complications of SS and SSD and merits further investigations.
Glycyrrhetinic Acid‐Induced MiR‐663a Alleviates Hepatic Stellate Cell Activation by Attenuating the TGF‐β/Smad Signaling Pathway
Authors: Guo Xin-Xin , Yang Wen-Na , Dong Ben-Sheng , Shang Jia-Wei , Su Shi-Bing , Yan Xiu-Li , Zhang Hui
Published: May 2020

Glycyrrhetinic acid (GA), a hydrolysate of glycyrrhizic acid from licorice root extract, has been used to treat liver fibrotic diseases. However, the molecular mechanism involved in the antifibrotic effects of GA remains unclear. The involvement of miR‐663a and its roles in TGF‐β‐1‐induced hepatic stellate cell (HSC) activation remains unclear. In this study, we investigated the roles of miR‐663a in the activation of HSCs and the antifibrosis mechanism of GA. MiR‐663a expression was downregulated in TGF‐β‐treated HSCs. The overexpression of miR‐663a inhibited HSC proliferation. TGF‐β‐1was confirmed as a direct target gene of miR‐663a. MiR‐663a alleviated HSC activation, concomitant with decreased expression of α‐smooth muscle actin (α‐SMA), human α2 (I) collagen (COL1A2), TGF‐β1, TGF‐βRI, Smad4, p‐Smad2, and p‐Smad3. GA upregulated miR‐663a expression and inhibited the TGF‐β/Smad pathway in HSCs. Further studies showed that miR‐663a inhibitor treatment reversed GA‐mediated downregulation of TGF‐β1, TGF‐βRI, Smad4, p‐Smad2, p‐Smad3, α‐SMA, and CoL1A2 in TGF‐β1‐treated HSCs. These results show that miR‐663a suppresses HSC proliferation and activation and the TGF‐β/Smad signaling pathway, highlighting that miR‐663a can be utilized as a therapeutic target for hepatic fibrosis. GA inhibits, at least in part, HSC proliferation and activation via targeting the miR‐663a/TGF‐β/Smad signaling pathway.
Numerical Study on the Characteristics and Effects of Gap Flow in Two Parallel Rotating Disks
Authors: Wang Jin , Xue Qilong , Liu Baolin , Li Fangtao , Zhang Zonghu
Published: May 2020

Rotating plane flow distributing pairs have been widely used in engineering. It is very important to reduce the frictional resistance between the pairs to improve the sensitivity and prolong service life. In this paper, the traditional rotating plane flow pair is improved, and the boss is introduced to keep the rotor and the stator in incomplete contact, and then a gap is formed between the flow pairs. The relationship between the pressure distribution and the friction resistance of the flow pairs is established. The theoretical mathematical model of the fluid movement between the gaps of the structure is built. Given the complexity of model analysis, the numerical analysis method is used to analyze the fluid motion in the structure. The height of the boss is proved to be the most important parameter of the structure, the increase of the boss’s height causes the pressure between the flow pairs to increase, and the pressure difference between regions gradually decreases, so the friction between the flow pairs will gradually decrease until reaching a stable value. The change of the boss’s diameter has little influence on the pressure distribution of the clearance, but as the diameter increases, the friction between the flow pairs will increase linearly. Once the opening width of the waist hole on the upper rotor is smaller than the radius of the discharge hole on the lower stator, the smaller the width, the higher the pressure, but when the opening width is larger than the radius of the discharge holes, the change of the width has no obvious influence on the pressure distribution and the friction.
Energy-Saving Virtual Machine Placement Method for User Experience in Cloud Environment
Authors: Pang Shanchen , Xu Kexiang , Wang Shudong , Wang Min , Wang Shuyu
Published: May 2020

Green computing focuses on the energy consumption to minimize costs and adverse environmental impacts in data centers. Improving the utilization of host computers is one of the main green cloud computing strategies to reduce energy consumption, but the high utilization of the host CPU can affect user experience, reduce the quality of service, and even lead to service-level agreement (SLA) violations. In addition, the ant colony algorithm performs well in finding suitable computing resources in unknown networks. In this paper, an energy-saving virtual machine placement method (UE-ACO) is proposed based on the improved ant colony algorithm to reduce the energy consumption and satisfy users’ experience, which achieves the balance between energy consumption and user experience in data centers. We improve the pheromone and heuristic factors of the traditional ant colony algorithm, which can guarantee that the improved algorithm can jump out of the local optimum and enter the global optimal, avoiding the premature maturity of the algorithm. Experimental results show that compared to the traditional ant colony algorithm, min-min algorithm, and round-robin algorithm, the proposed algorithm UE-ACO can save up to 20%, 24%, and 30% of energy consumption while satisfying user experience.
Precise Active Seeding Downforce Control System Based on Fuzzy PID
Authors: Li Baosheng , Tan Yu , Chen Jian , Liu Xingxing , Yang Shenghui
Published: May 2020

Soil compaction is an important procedure of precision seeding operation. In this paper, a precise downforce control system based on fuzzy PID was proposed in order to improve the quality of the soil compaction and the accuracy of setting working parameters. The conventional mechanism of seeders for soil compaction was optimised. The compressing spring of the compaction mechanism was replaced by a linear motor, which is actively controlled to adjust downforce in real time. A force sensor was connected in series with the linear motor to detect the actual downforce from a press wheel acting on soil. The detected downforce was employed as feedback for the fuzzy PID model. A slave real-time control system was constructed by using an STM32 microcontroller. A user interface was designed for the portable master computer system based on the ForLinx embedded platform to facilitate the setting of target downforce and display the actual downforce in real time. Meanwhile, it was able to adjust the system for different operating requirements, such as soil stiffness, moisture, and crop species. Experiments were conducted on a soil bin, and the results indicated that the active control system has better performance than the conventional passive system in downforce control. The downforce was stable with a variance less than 2.6% under different conditions, and it was 8.11% less than the conventional passive system.
The Propagation of Landslide‐Generated Impulse Waves and Their Impacts on the Moored Ships: An Experimental Investigation
Authors: Mu Ping , Wang Pingyi , Han Linfeng , Wang Meili , Meng Caixia , Cheng Zhiyou , Xu Haiyong
Published: May 2020

The effective prevention and reduction of the hazardous impact of landslide‐generated impulse waves on the moored ships are crucial for the sustainable operation of the reservoirs. Although the investigations of landslide‐generated impulse waves have been widely studied in the past decades, few efforts involved their impacts on the moored ships. The authors in this paper specifically examine the hazardous impact of the impulse waves on the moored ships by applying the physical experiments. Considering that the impulse wave was an external force acting on the mooring line, the impulse wave generation, propagation, and its impact on the moored ships are hence explored in detail. The results indicate that the impact of impulse waves on the moored ships was mainly due to the first wave amplitude and height, and an exponential function relationship between the relative wave height and wave crest amplitude was revealed. Furthermore, the attenuation of the maximum wave crest amplitude was approximated by a power exponential function. On this basis, the mooring tension could be calculated based on the linear relationship between the mooring tension and wave height. Ultimately, the safety of the moored ships in the port can be evaluated.
Knowledge, Attitude, and Preventive Practices towards Sexually Transmitted Infections among Preparatory School Students in West Gojjam Zone, Ethiopia
Authors: Kassie Ayalnesh Asmamaw , Gudayu Temesgen Worku , Araya Bilen Mekonnen
Published: May 2020

Background. Sexually transmitted infections are major public health concerns that mostly affect adolescents and young people. Hence, the aim of this study was to assess students’ knowledge, attitude, and preventive practice towards sexually transmitted infections and the associated factors. Methods. A school-based cross-sectional study was conducted from October 24 to November 4, 2018. A sample size of 845 was calculated and a 1-stage sampling technique was employed. Data were collected through a self-administered questionnaire. The data were entered into Epi-Info 7.2 and analyzed using IBM SPSS version 25 software. The descriptive result was presented in text, figure, and tables. Also, bivariate and multivariable logistic regression analyses were done to identify associated factors. Then the adjusted odds ratio and its 95% confidence interval were computed. And a p value of <0.05 was considered to assert statistical significance. Results. Half of the respondents (50.5%) had good knowledge on sexually transmitted infections. Also, 46.4% of students had a good preventive practice. However, only 38.4% of students had an appropriate attitude towards sexually transmitted infections. Being a male (AOR: 1.58 (95% CI: (1.19, 2.09)) and having employed father (AOR: 1.97 (95% CI: (1.18, 3.30)) predicted good knowledge. Similarly, secondary and above level of paternal education (AOR: 2.16 (95% CI: (1.28, 3.64)) and having a farmer father (AOR: 1.77 (95% CI: (1.04, 3.02)) predicted appropriate attitude. Predictors of preventive practices included elder age (AOR: 2.33 (95% CI: (1.27, 4.28)), never had sexual intercourse (AOR: 1.44 (95% CI: (1.07, 1.94)), and having good knowledge on STIs (AOR: 1.53 (95% CI: (1.16, 2.02)). Conclusion. The proportion of students that had good knowledge, appropriate attitude, and good preventive practice towards STIs were low. Personal and parental factors predicted students’ knowledge, attitude, and preventive practices. Hence, creating awareness need to be strengthened.
Inflammation and Oxidative Stress in Multiple Sclerosis: Consequences for Therapy Development
Authors: Pegoretti Valentina , Swanson Kathryn A. , Bethea John R. , Probert Lesley , Eisel Ulrich L. M. , Fischer Roman
Published: May 2020

CNS inflammation is a major driver of MS pathology. Differential immune responses, including the adaptive and the innate immune system, are observed at various stages of MS and drive disease development and progression. Next to these immune-mediated mechanisms, other mediators contribute to MS pathology. These include immune-independent cell death of oligodendrocytes and neurons as well as oxidative stress-induced tissue damage. In particular, the complex influence of oxidative stress on inflammation and vice versa makes therapeutic interference complex. All approved MS therapeutics work by modulating the autoimmune response. However, despite substantial developments in the treatment of the relapsing-remitting form of MS, approved therapies for the progressive forms of MS as well as for MS-associated concomitants are limited and much needed. Here, we summarize the contribution of inflammation and oxidative stress to MS pathology and discuss consequences for MS therapy development.
Development of Nanozyme-Labeled Biomimetic Immunoassay for Determination of Sulfadiazine Residue in Foods
Authors: He Jingbo , Zhang Li , Xu Longhua , Kong Feifan , Xu Zhixiang
Published: May 2020

The excessive use and ingestion of residues of sulfonamides harm the human body and the environment. To meet the requirements of the maximum residue limit specified by the Ministry of Agriculture of China, a rapid detection method urgently needs to be developed. In the present study, a molecularly imprinted polymer (MIP) that could selectively recognize sulfadiazine (SDZ) was prepared using SDZ as the template molecule and methacrylic acid as the functional monomer. Using MIP as biomimetic antibody and Au@Pt@SiO2 nanozyme as a marker, a new biomimetic immunoassay was developed to detect sulfadiazine. Under the optimal conditions, the limit of detection (IC15) and sensitivity (IC50) of this method were 0.09 and 6.1 mg/L, respectively. To determine the accuracy of this method, honey and milk samples spiked with sulfadiazine were analyzed, with recoveries in the range of 70.8%-90.2%. The method was also used for the quantitative analysis of sulfadiazine residues in milk powder and milk samples, producing results which correlated well with those obtained by high-performance liquid chromatography.
Huang‐Pu‐Tong‐Qiao Formula Ameliorates Tau Phosphorylation by Inhibiting the CaM‐CaMKIV Pathway
Authors: Ye Shu , Cai Biao , Zhou Peng , Wang Guoquan , Gao Huawu , Hua Rupeng , You Liangzhen , Yao Yongchuan , Wang Yan , Shen Guoming
Published: May 2020

Alzheimer’s disease (AD) is a complex neurodegenerative disease. It is a chronic, lethal disease in which brain function is severely impaired and neuronal damage is irreversible. Huang‐Pu‐Tong‐Qiao (HPTQ), a formula from traditional Chinese medicine, has been used in the clinical treatment of AD for many years, with remarkable effects. However, the neuroprotective mechanisms of HPTQ in AD have not yet been investigated. In the present study, we used AD models in vivo and in vitro, to investigate both the neuroprotective effect of HPTQ water extracts (HPTQ‐W) and the potential mechanisms of this action. For the in vivo study, after HPTQ intervention, the Morris water maze test was used to examine learning and memory in rats. Transmission electron microscopy and immunofluorescence methods were then used to investigate neuronal damage. For the in vitro experiments, rat primary hippocampal neurons were cultured and cell viability was examined by 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide. Additionally, mRNA levels of CaM, CaMKK, CaMKIV, and tau were examined using qRT‐PCR, and protein expression of CaM, CaMKK, p‐CaMKIV, and p‐tau were examined using western blot. In vivo, we revealed that HPTQ significantly improved learning and memory deficits and attenuated neuronal damage in the AD rat model. Furthermore, in vitro results showed that HPTQ significantly increased cell viability in the AD cell model. We also demonstrated that HPTQ significantly decreased the mRNA levels of CaM, CaMKK, CaMKIV, and tau and significantly decreased the protein expressions of CaM, CaMKK, p‐CaMKIV, and p‐tau. In conclusion, our results indicated that HPTQ improved cognition and ameliorated neuronal damage in AD models and implicated a reduction in tau phosphorylation caused by inhibition of the CaM‐CaMKIV pathway as a possible mechanism.
Comparative Effectiveness of Different Combinations of Treatment Interventions in Patients with Stroke at the Convalescence Stage Based on the Markov Decision Process
Authors: Shen Yejing , Hu Mengyun , Chen Qianglong , Zhang Yanyang , Liang Junying , Lu Tingting , Ma Qinqin , Ma Ruijie
Published: May 2020

Objective. The objective of this study was to compare the effectiveness of different combinations of interventions in patients with stroke at the convalescence stage based on the electronic health records (EHRs) by using the Markov decision process (MDP) theory and explore the feasibility of the Markov model in the real‐world study (RWS). Methods. Screening was conducted for patients with stroke at the convalescence stage who were admitted to the Third Affiliated Hospital of Zhejiang Chinese Medical University from January 2012 to January 2017 based on the EHRs. The relevant clinical data were extracted, and the appropriate conversion was made (state‐action‐reward) according to the Markov model. The transformed data were analysed and solved by the MDP to obtain the best interventions for patients with various stroke recovery periods. Results. 926 patients with stroke at the convalescence stage were initially selected. And according to the inclusion exclusion criteria, 854 patients were screened. Through the MDP, we obtained the following results: (1)when the patients with stroke at the convalescence stage have a medical history, but no complications, and mild neurological impairment, ≥66‐year‐ and 18–45‐year‐old patients are advised to choose acupuncture treatment. 46–65‐year‐old patients are advised to choose rehabilitation treatment. When patients with moderate to severe neurological impairment, patients are advised to choose rehabilitation, Chinese herbal decoction, and acupuncture combined therapy. (2) Without complications or medical history, patients who are ≥ 66 years old are recommended to choose rehabilitation treatment when the nerve function impairment is mild; rehabilitation and acupuncture treatment are recommended when moderate and severe injuries are caused. (3) The combination of rehabilitation, Chinese herbal decoction, and acupuncture treatment is recommended for patients with phlegm and blood stasis. Acupuncture treatment is recommended for patients with mild impairment of nerve function in qi deficiency and blood stasis type. Rehabilitation, Chinese herbal decoction, and acupuncture treatment are recommended for moderate‐severe injuries. Conclusions. The MDP makes it possible to study the effectiveness of various treatment methods in stroke patients who are at the convalescence stage. Further exploratory studies using MDP theory in other areas in which complex interventions are common would be worthwhile.
Direct Cost of Parkinson’s Disease: A Real-World Data Study of Second-Line Therapies
Authors: Gomez-Inhiesto Elisa , Acaiturri-Ayesta María Teresa , Ustarroz-Aguirre Iker , Camahuali Diana , Urtaran-Laresgoiti Maider , Basabe-Aldecoa Marisol , Nuño-Solinís Roberto , Urizar Elena
Published: May 2020

Parkinson’s disease is one of the main reasons for neurological consultation in Spain. Due to the nature of the disease, it impacts patients, families, and caregivers. Parkinson’s disease is a degenerative disease with no cure, although second-line therapies have recently improved the quality of life of patients in advanced stages. The aim of this study was to analyse the costs of the following therapies: deep brain stimulation (DBS), continuous duodenal levodopa/carbidopa infusion (CDLCI), and continuous subcutaneous apomorphine infusion (CSAI). The methodology used was based on real-world data obtained from an integrated healthcare organization in the Basque Country from 2016 to 2018. This bottom-up retrospective approach only took into account the healthcare perspective. The results revealed the annual cost over 3 years and the projected cost for an additional 2 years. The total costs for 5 years of treatment were as follows: €53,217 for DBS, €208,163 for CDLCI, and €170,591 for CSAI. These costs are in line with those found in the available literature on the subject. Additionally, the analysis provided details of the different costs incurred during intervention with the therapies and compared the costs to those reported in other studies.
Exact Solutions for the Conformable Space-Time Fractional Zeldovich Equation with Time-Dependent Coefficients
Authors: Injrou Sami
Published: May 2020

The aim of this paper is to improve a sub-equation method to solve the space-time fractional Zeldovich equation with time-dependent coefficients involving the conformable fractional derivative. As result, we obtain three families of solutions including the hyperbolic, trigonometric, and rational solutions. These solutions may be helpful to explain several phenomena in chemistry, including the combustion process. The study shows that the used method is effective and reliable and can be utilized as a substitution to construct new solutions of different types of nonlinear conformable fractional partial differential equations (NFPDEs) with variable coefficients.
Interstitial Pregnancy in the Third Trimester with Severe Preeclampsia: A Case Report and Literature Review
Authors: Nagayama Shiho , Takahashi Hironori , Tozawa Shohei , Narumi Risa , Usui Rie , Ohkuchi Akihide , Matsubara Shigeki
Published: May 2020

An interstitial pregnancy that continues beyond the second trimester is a rare phenomenon. We report a patient with an interstitial pregnancy undiagnosed until the third trimester. A multiparous woman was referred to us because of preeclampsia at 26 weeks of gestation. The placental position was the right fundus, and color Doppler ultrasound revealed myometrial thinning and subplacental hypervascularity, leading to a suspicion of placenta accreta spectrum (PAS). Emergency cesarean section was performed at 281/7 weeks of gestation due to severe preeclampsia. The right tubal horn to the isthmus of the fallopian tube bulged with placental adhesion and a part of the tube had ruptured, with the omentum adhering to the ruptured part. Interstitial and tubal isthmic pregnancy with uterine rupture was diagnosed.