bluuebunny/crossref_metadata_2025 huggingface dataset:
Experimental Study and Numerical Simulation of the Intermittent Feed High-Speed Grinding of TC4 Titanium Alloy
Authors: Yi Jun , Zhou Wei , Deng Zhaohui
Published: July 2019

This paper proposes intermittent feed high-speed grinding, which shows considerable advantages in terms of reducing grinding temperature, relieving grinding wheel blockage and improving workpiece surface integrity. In this grinding, the continuous feed mode of the workpiece is changed into the normal feed + fast retreat reciprocating feed mode by a fast linear feed worktable. By reasonably setting the normal feed distance of single grinding, the action time of the grinding wheel and workpiece is reduced, so that the grinding heat transfer process does not reach a stable state, reducing the grinding temperature during single grinding. Besides this, the surface temperature is cooled to nearly room temperature and the grinding wheel is flushed by the timely retreating of the grinding wheel to allow the grinding fluid to enter the grinding zone fully, which greatly reduces the phenomenon of heat accumulation and grinding wheel loading. An intermittent feed high-speed grinding experiment on Ti-6Al-4V (TC4) titanium alloy was systematically carried out, and the influence of the grinding parameters on grinding force and grinding temperature was deeply analyzed. The instantaneous grinding temperature field and thermal stress field of TC4 titanium alloy in intermittent feed high-speed grinding were constructed with the finite element method. The surface morphology of the grinding wheel and TC4 titanium alloy specimens after intermittent feed grinding were analyzed and were compared with those after traditional continuous grinding. It was found that the curves of the grinding force and temperature varied with time in the process of machining, consisting of many “pulse” peaks. Under the same grinding parameters, the magnitude of the grinding force is the same as that of continuous grinding. In a certain range, the grinding temperature is greatly affected by the single feed distance and the interval time. The numerical simulation results are in good agreement with the experimental results, and the error is controlled within 12%. Compared with traditional high-speed grinding, under the same process parameters, the grinding temperature is greatly reduced, the surface integrity of the workpiece is better, and the clogging of the grinding wheel is greatly reduced.
Residual Stress, Microstructure and Mechanical Properties in Thick 6005A-T6 Aluminium Alloy Friction Stir Welds
Authors: Liu Xiaolong , Xie Pu , Wimpory Robert , Li Wenya , Lai Ruilin , Li Meijuan , Chen Dongfeng , Liu Yuntao , Zhao Haiyan
Published: July 2019

Plates (37 mm thick) of 6005A-T6 aluminum alloy were butt joined by a single-sided and double-sided friction stir welding (FSW). The 3D residual stresses in the joints were determined using neutron diffraction. The microstructures were characterized by a transmission electron microscope (TEM) and electron backscatter diffraction (EBSD). In the single-sided FSW specimen, there were acceptable mechanical properties with a tensile strength of 74.4% of base metal (BM) and low residual stresses with peak magnitudes of approximately 37.5% yield strength of BM were achieved. The hardness is related to the grain size of the nugget zone (NZ), and in this study, precipitations were dissolved due to the high heat input. In the double-sided FSW specimen, there were good mechanical properties with a tensile strength of 80.8% of BM, but high residual stresses with peak magnitudes of approximately 70% yield strength of BM were obtained. The heat input by the second pass provided an aging environment for the first-pass weld zone where the dissolved phases were precipitated and residual stresses were relaxed.
Design for Novel Hot-Work Die Steel by Thermodynamic Calculation and Microstructural Examination
Authors: Zhang Zunjun , Zhang Jishan , Yao Zhihao , Xie Guoliang , Lian Yong , Ma Minyu , Zhao Chao , Huang Jinfeng
Published: July 2019

In this paper, a new type of hot-work die steel with excellent high-temperature mechanical properties at 700 °C was designed based on the traditional 25Cr3Mo3NiNb steel with the help of Thermo-calc software. The effects of C, Cr, Mo, W and V on the types and mass fractions of carbides were studied. Phase diagram calculation revealed that with the increase of V and W contents and the decrease of Cr content, the precipitation temperature and the mass fraction of M23C6 carbides decreased. Meanwhile, the mass fraction of MC carbides increased as the Mo content decreased. Based on the thermodynamic calculation, new material 25Cr3Mo2NiWVNb steel was designed. Compared to the 25Cr3Mo3NiNb steel, more finely dispersed MC and M2C carbides with high thermal stability, as well as fewer M23C6 carbides with low thermal stability, were precipitated in the new steel. The high-temperature tensile showed that the new steel showed high thermal stability and strength even at 700 °C. The high-temperature strengthening effect might be ascribed to the fine and stable nano-scale MC and M2C carbides which precipitated during tempering.
Modeling the Effect of Different Support Structures in Electron Beam Melting of Titanium Alloy Using Finite Element Models
Authors: Umer Usama , Ameen Wadea , Abidi Mustufa Haider , Moiduddin Khaja , Alkhalefah Hisham , Alkahtani Mohammed , Al-Ahmari Abdulrahman
Published: July 2019

Electron beam melting (EBM) technology is a novel additive manufacturing (AM) technique, which uses computer controlled electron beams to create fully dense three-dimensional objects from metal powder. It gives the ability to produce any complex parts directly from a computer aided design (CAD) model without tools and dies, and with variety of materials. However, it is reported that EBM has limitations in building overhang structures, due to the poor thermal conductivity for the sintered powder particles under overhang surfaces. In the current study, 2D thermo-mechanical finite element models (FEM) are developed to predict the stresses and deformation associated with fabrication of overhang structures by EBM for Ti-6Al-4V alloy. Different support structure geometries are modeled and evaluated. Finally, the numerical results are validated by experimental work.
Study on Multi-Step Creep Aging Behavior of Al-Li-S4 Alloy
Authors: Ma Yunlong , Xia Feng , Zhan Lihua , Xu Yongqian
Published: July 2019

Creep age forming (CAF) is a new technology developed for manufacturing large aluminum components in the aerospace industry. Aluminum–lithium alloys may be used in aerospace components because of their high modulus, specific strength and specific stiffness. Therefore, the creep deformation, mechanical properties and aging precipitation of Al-Li-S4 alloy under CAF conditions were studied. It was found that the creep behavior presents double steady state creep stages during the creep aging process. With the increase of stress level, the first steady creep rate increased, but the second steady creep rate was slightly reduced. Coincidentally, in the first steady state creep stage, the yield strength of the studied alloy also showed a slow increase stage. TEM observation showed that Al-Li-S4 alloy mainly contains two precipitation phases, T1 phase and θ’ phase. A few precipitates form during the first steady creep stage. Then, a lot of nucleation and growth of T1 phase resulted in rapid increase of yield strength. At the same time, the increase of stress level effectively inhibited the growth of T1 phase, which resulted in these strengthening phases being more uniform, and thus improved the mechanical properties of materials. On this basis, the relationship between the multi-step behaviors of creep, mechanical properties and aging precipitates are discussed. It is considered that the main reasons for the multi-step phenomenon of creep and mechanical properties are strongly related to the nucleation, growth and distribution of T1 phase.
Experimental Determination of Electronic Density and Temperature in Water-Confined Plasmas Generated by Laser Shock Processing
Authors: Colón Cristóbal , de Andrés-García María Isabel , Moreno-Díaz Cristina , Alonso-Medina Aurelia , Porro Juan Antonio , Angulo Ignacio , Ocaña José Luis
Published: July 2019

In this work, diagnoses of laser-induced plasmas were performed in several Laser Shock Processing (LSP) experiments using the Balmer Hα-line (656.27 nm) and several Mg II spectral lines. A Q-switched laser of Nd:YAG was focused on aluminum samples (Al2024-T351) in LSP experiments. Two methods were used to diagnose the plasma. The first method, which required two different experiments, was the standard for establishing the electronic temperature through the use of a Boltzmann Plot with spectral lines of Mg II and self-absorption correction. The Stark width of the Balmer Hα-line was used to determine the electron density in each of the cases studied. The second method had lower accuracy, but only required an experimental determination. Two parameters, the electronic temperature and the electron density, were obtained with the aid of the Hα-line in a single data acquisition process. The order of magnitude of the temperature obtained from this last method was sufficiently close to the value obtained by the standard method (within a factor lower than 2.0), which is considered to be important in order to allow for its possible use in industrial conditions.
Micro Vacuum Chuck and Tensile Test System for Bio-Mechanical Evaluation of 3D Tissue Constructed of Human Induced Pluripotent Stem Cell-Derived Cardiomyocytes (hiPS-CM)
Authors: Uesugi Kaoru , Shima Fumiaki , Fukumoto Ken , Hiura Ayami , Tsukamoto Yoshinari , Miyagawa Shigeru , Sawa Yoshiki , Akagi Takami , Akashi Mitsuru , Morishima Keisuke
Published: July 2019

In this report, we propose a micro vacuum chuck (MVC) which can connect three-dimensional (3D) tissues to a tensile test system by vacuum pressure. Because the MVC fixes the 3D tissue by vacuum pressure generated on multiple vacuum holes, it is expected that the MVC can fix 3D tissue to the system easily and mitigate the damage which can happen by handling during fixing. In order to decide optimum conditions for the size of the vacuum holes and the vacuum pressure, various sized vacuum holes and vacuum pressures were applied to a normal human cardiac fibroblast 3D tissue. From the results, we confirmed that a square shape with 100 µm sides was better for fixing the 3D tissue. Then we mounted our developed MVCs on a specially developed tensile test system and measured the bio-mechanical property (beating force) of cardiac 3D tissue which was constructed of human induced pluripotent stem cell-derived cardiomyocytes (hiPS-CM); the 3D tissue had been assembled by the layer-by-layer (LbL) method. We measured the beating force of the cardiac 3D tissue and confirmed the measured force followed the Frank-Starling relationship. This indicates that the beating property of cardiac 3D tissue obtained by the LbL method was close to that of native cardiac tissue.
Real Time Electronic Feedback for Improved Acoustic Trapping of Micron-Scale Particles
Authors: Clark Charles , Farmehini Vahid , Spiers Liam , Woolf M. , Swami Nathan , Landers James
Published: July 2019

Acoustic differential extraction has been previously reported as a viable alternative to the repetitive manual pipetting and centrifugation steps for isolating sperm cells from female epithelial cells in sexual assault sample evidence. However, the efficiency of sperm cell isolation can be compromised in samples containing an extremely large number of epithelial cells. When highly concentrated samples are lysed, changes to the physicochemical nature of the medium surrounding the cells impacts the acoustic frequency needed for optimal trapping. Previous work has demonstrated successful, automated adjustment of acoustic frequency to account for changes in temperature and buffer properties in various samples. Here we show that, during acoustic trapping, real-time monitoring of voltage measurements across the piezoelectric transducer correlates with sample-dependent changes in the medium. This is achieved with a wideband peak detector circuit, which identifies the resonant frequency with minimal disruption to the applied voltage. We further demonstrate that immediate, corresponding adjustments to acoustic trapping frequency provides retention of sperm cells from high epithelial cell-containing mock sexual assault samples.
Insights into the Potential of the Atlantic Cod Gut Microbiome as Biomarker of Oil Contamination in the Marine Environment
Authors: Walter Juline M. , Bagi Andrea , Pampanin Daniela M.
Published: July 2019

Background: Microorganisms are widespread in all environments, including in and on animal bodies. The gut microbiome has an essential influence on fish health, and is affected by several persistent and harmful organic and inorganic contaminants. Considering the shifts in gut microbiota composition observed in those studies, we hypothesized that certain microbial groups in the gut can serve as indicators of pollution. To test this hypothesis, we explored the possibility of identifying key microbial players that indicate environmental contamination. Methods: Published 16S rRNA gene amplicon sequencing data generated from the gut microbiota of Atlantic cod caught in geographically different Norwegian waters were used for bacterial diversity comparison. Results: Different microbiomes were identified between the northern Norway and southern Norway samples. Several bacterial genera previously identified as polycyclic aromatic hydrocarbon degraders were present only in the samples collected in the southern Norway area, suggesting fish contamination with oil-related compounds. Conclusions: The results contribute to the identification of bacterial taxa present in the Atlantic cod gut that indicate fish exposure to contaminants in the marine environment.
Phylogenetic and Molecular Profile of Staphylococcus aureus Isolated from Bloodstream Infections in Northeast Brazil
Authors: Monteiro Andrea de S. , Pinto Bruna L. S. , Monteiro Joveliane de M. , Ferreira Rômulo M. , Ribeiro Patrícia C. S. , Bando Silvia Y. , Marques Sirlei G. , Silva Luís C. N. , Neto Wallace R. Nunes , Ferreira Gabriella F. , Bomfim Maria Rosa Q. , Abreu Afonso G.
Published: July 2019

Staphylococcus aureus is a notorious human pathogen associated with serious nosocomial and community-acquired infections, such as pneumonia, meningitis, endocarditis, toxic shock syndrome, and sepsis, among others. The objective of this study was to investigate the molecular profile, antimicrobial resistance, and clonal diversity of S. aureus isolated from the bloodstream. The determination of the minimum inhibitory concentration (MIC) of the antimicrobial was performed by an automated method. The presence of several virulence and resistance genes was evaluated by PCR. In addition, multilocus sequence typing (MLST) was used to analyze the clonal diversity of S. aureus. A high resistance to oxacillin (78%), clindamycin (78%), erythromycin (70%), ciprofloxacin (61%), and gentamicin (52%) was observed among the isolates. In most of them, the following virulence genes were detected: hlb (83%), ebpS (61%), icaA (57%), fnbpA (17%), and clfA (13%). Only one isolate carried the pvl gene. MLST analysis identified five new sequence types (STs): 5429, 5430, 5431, 5432, and 5433, as well as another seven—ST5, ST97, ST398, ST101, ST30, ST461, and ST2779—among the remaining strains. These seven STs and the four new STs are clustered in four clonal complexes: CC1, CC2, CC7, and CC17. Phylogenetic analysis showed the genetic relationship of the five new ST strains with another 18 strains. Altogether, these analyses indicate the horizontal transfer acquisition of virulence factor genes and multidrug resistance.
Genomic Insights of Dyadobacter tibetensis Y620-1 Isolated from Ice Core Reveal Genomic Features for Succession in Glacier Environment
Authors: Shen Liang , Liu Yongqin , Wang Ninglian , Adhikari Namita Paudel
Published: July 2019

Glaciers have been recognized as biomes, dominated by microbial life. Many novel species have been isolated from glacier ecosystems, and their physiological features are well characterized. However, genomic features of bacteria isolated from the deep ice core are poorly understood. In this study, we performed a comparative genomic analysis to uncover the genomic features of strain Dyadobacter tibetensis Y620-1 isolated from a 59 m depth of the ice core drilled from a Tibetan Plateau glacier. Strain D. tibetensis Y620-1 had the smallest genome among the 12 cultured Dyadobacter strains, relatively low GC content, and was placed at the root position of the phylogenomic tree. The gene family based on a nonmetric multidimensional scaling (NMDS) plot revealed a clear separation of strain D. tibetensis Y620-1 from the reference strains. The genome of the deep ice core isolated strain contained the highest percentage of new genes. The definitive difference is that all genes required for the serine-glyoxylate cycle in one-carbon metabolism were only found in strain D. tibetensis Y620-1, but not in any of the reference strains. The placement of strain D. tibetensis Y620-1 in the root of the phylogenomic tree suggests that these new genes and functions are of ancient origin. All of these genomic features may contribute to the survival of D. tibetensis Y620-1 in the glacier.
Application of Falcon Centrifuge as a Cleaner Alternative for Complex Tungsten Ore Processing
Authors: Foucaud Yann. , Dehaine Quentin , Filippov Lev. , Filippova Inna
Published: July 2019

Scheelite (CaWO4) is one of the main raw material for the production of tungsten. It is usually encountered in skarn deposits where it is commonly associated with other calcium minerals as fluorite, apatite, and calcium silicates. Worldwide, scheelite is upgraded to the chemical grades by direct flotation, but the separation efficiency remains limited due to similar flotation behaviors of scheelite and gangue minerals with fatty acid. The only solutions used to overcome this issue involve high energy consumption or ecotoxic reagents. In the present study, a novel method based on the use of a centrifugal Falcon concentrator was investigated to perform an efficient elimination of gangue minerals and fine particles as well as an acceptable scheelite recovery enabling a decrease of the flotation reagents consumption. The performances of the two types of laboratory Falcon bowls, Falcon UltraFine (UF) and Falcon Semi-Batch (SB), were modeled using the design of experiments (DoE) methodology, which allowed to determine the best operating parameters for each bowl. The separation performances were mainly affected by the rotary speed and the pulp density for the Falcon UF and by the rotary speed and the fluidization pressure for the Falcon SB. Due to the fluidization pressure, the Falcon SB exhibited higher gangue minerals rejection with slightly lower recoveries than the Falcon UF. Overall, the optimized Falcon SB test allowed to reach 71.6%, 22.6%, 17.2%, and 12.6% for scheelite, calcium salts, dense calcium silicates, and light non-calcic silicates respectively while the desliming efficiency reached 98.8%. For comparison purposes, a classical hydrocyclone allowed to attain 89.1%, 89.3%, 79.5%, and 76.5% for scheelite, calcium salts, dense calcium silicates, and light non-calcic silicates respectively while the desliming efficiency reached 52.0%. Theses results can be used reliably to assess the separation performances of an industrial Falcon C which can be regarded, along with Falcon SB, as a sustainable and efficient gangue rejection method for complex W skarn ore, which allows the use of environmentally friendly reagents during downstream flotation stages.
Modeling of REE and Fe Extraction from a Concentrate from Araxá (Brazil)
Authors: Nascimento Marisa , Lemos Flávio , Guimarães Rogério , Sousa Clóvis , Soares Paulo
Published: July 2019

The study aimed to employ a comprehensive methodology for the acid processing of a rare earth element (REE) concentrate obtained from the ore from Araxá (MG-Brazil). The most important process variables have been identified and their levels determined to maximize REE extraction (%RE) and minimize Fe extraction (%Fe). The thermodynamic analysis showed that the roasting temperature (TF) is crucial for the control of Fe solubilization in the aqueous leaching step of the acid processing. A statistic design of laboratory experiments and a process optimization method were applied to address the interaction among the process variables. Experimental results showed that a TF of about 700 °C can significantly reduce the Fe concentration in the aqueous leaching liquor. Mathematical models were proposed to predict the effect of process variable on REE and Fe extraction of the concentrate. A multi-objective technique was employed for optimization of chemical processing and the best conditions were reached for roasting temperature (TF) = 700 °C, acid to sample mass ratio (ACs) = 0.8 and leaching time (tL) = 20 min, which led to %RE = 96.91% and %Fe = 21.69%.
Evaluation of the Sorption Potential of Mineral Materials Using Tetracycline as a Model Pollutant
Authors: Cuevas Jaime , Dirocie Nisael , Yunta Felipe , García Delgado Carlos , González Santamaría Daniel E. , Ruiz Ana Isabel , Fernández Raúl , Eymar Enrique
Published: July 2019

Tetracycline (TC) is among the most used antibiotics in animal feedstock in the EU. Antibiotics’ persistence as emerging pollutants in the environment is evidenced by their long half-life in residual organic-mineral sediments and waters. The risk associated with this persistence favours antibiotic-resistant microbiota, affecting human health and ecosystems. The purpose of the present work is to assess the adsorption of TC into natural clay minerals, synthetic iron hydroxides and calcined sewage sludge. TC adsorption isotherms were performed in three replicated batch tests at three different pH values (4, 6, 8) and TC concentrations (33–1176 mg·L−1). X-Ray diffraction (XRD) mineralogy, cation exchange capacity (CEC), Brunauer, Emmett and Teller specific surface area (BET-SSA) and point of zero charge salt effect (PZSE) were determined for the characterization of materials. Sorption was analysed by means of fitting Langmuir and Freundlich adsorption models, which showed good fitting parameters for the studied materials. Low-charge montmorillonite (LC Mnt) is displays the best sorption capacity for TC at maximum TC concentration (350–300 mgTC·g−1) in the whole range of pH (4–8). Sepiolite and smectites adsorbed 200–250 mgTC·g−1, while illite, calcined sludge or iron hydroxides present the lowest adsorption capacity (<100 mgTC·g−1). Nevertheless, illite, sepiolite and ferrihydrite display high adsorption intensities at low to medium TC concentrations (<300 mg·L−1), even at pH 8, as is expected in wastewater environmental conditions.
The Chemical Composition and Surface Texture of Transparent Heavy Minerals from Core LQ24 in the Changjiang Delta
Authors: Yue Wei , Yue Xiyuan , Panwar Sugandha , Zhang Lingmin , Jin Bingfu
Published: July 2019

The assessment of textural and compositional modifications of detrital sediments is required to reconstruct past source to sink dynamics. The Changjiang Delta is an ideal location to study the sedimentary environment from the Pliocene to Quaternary transition. In the present study, we aim to decipher the response of heavy minerals to mechanical wear and chemical weathering since the Pliocene. With the application of a scanning electron microscope and an electron probe, the geochemistry and surface texture of different heavy minerals (amphibole, epidote, and tourmaline groups) with grain-size fractions of 32–63 µm and 63–125 µm were studied. The result shows that the surface texture of unstable minerals (amphibole, epidote) changed under strong chemical weathering in the Pliocene sediments. By contrast, unstable minerals of the Pleistocene sediments are relatively fresh and similar to those of the modern Changjiang sediment. The stable mineral tourmaline does not exhibit morphology changes in different chemical weathering conditions. No effect of grain size on geochemical composition is noticed. The single minerals of very fine sand and coarse silt show similar geochemical and morphological features. The integration of mineralogy, geochemical data, and grain size parameters yield a more precise understanding of the physical and chemical response of heavy minerals to different weathering conditions. The outcome of the study is also helpful in deciphering sediment provenance changes and environmental changes in the Changjiang basin.
Cold-Pressing Olive Oil in the Presence of Cryomacerated Leaves of Olea or Citrus: Nutraceutical and Sensorial Features
Authors: Sanmartin Chiara , Taglieri Isabella , Macaluso Monica , Sgherri Cristina , Ascrizzi Roberta , Flamini Guido , Venturi Francesca , Quartacci Mike Frank , Luro François , Curk Franck , Pistelli Luisa , Zinnai Angela
Published: July 2019

The nutraceutical properties of extra-virgin olive oil (EVOO) can be further improved by the addition of olive leaves during olive pressing. However, while Citrus leaves are rich sources of bioactive substances, no data are available in the literature about the effect of Citrus leaf addition on the nutraceutical and sensorial profiles of olive oil. This study aimed at comparing the chemical and sensorial qualities of olive oils obtained from ripe olives pressed together with either Olea or Citrus spp. (lemon or orange) cryomacerated leaves. General composition parameters as well as major antioxidants and antioxidant activity were measured. A panel test evaluation, as well as headspace volatile characterization (headspace solid phase microextraction, HS-SPME), were also performed. All data were compared with an EVOO extracted from the same olive batch used as control. It was possible to obtain Leaf Olive Oils (LOOs) characterized by a higher (p < 0.05) content of antioxidants, compared to the control sample, and the highest oleuropein concentration was detected in the olive oil extracted in presence of olive leaf (+50% in comparison with the control). All the LOOs showed a higher smell complexity and the scent of ripe fruit was generally mitigated. Lemon and olive LOOs showed the best smell profile.
Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides
Authors: Que Chuqiang , Huang Peipei , Yang Zhanhui , Chen Ning , Xu Jiaxi
Published: July 2019

The intramolecular C-H insertions of carbenes derived from 2-diazo-2-sulfamoylacetamides were studied. 2-Diazo-2-sulfamoylacetamides were first prepared from chloroacetyl chloride and secondary amines through acylation followed by sequential treatments with sodium sulfite, phosphorus oxychloride, secondary amines, and 4-nitrobenzenesulfonyl azide. The results indicate that: (1) 2-diazo-N,N-dimethyl-2-(N,N-diphenylsulfamoyl)acetamide can take the formal aromatic 1,5-C-H insertion in its N-phenylsulfonamide moiety to afford the corresponding 1,3-dihydrobenzo[c]isothiazole-3-carboxamide 2,2-dioxide derivative; (2) no aliphatic C-H insertions occur for 2-diazo-2-(N,N-dialkylsulfamoyl)acetamides; and (3) for 2-diazo-N-phenyl-2-(N-phenylsulfamoyl)acetamides, the formal aromatic 1,5-C-H insertion in the N-phenylacetamide moiety is favorable to afford the corresponding 3-sulfamoylindolin-2-one derivatives as sole or major products. The intramolecular competitive aromatic 1,5-C-H insertion reactions of 2-diazo-2-sulfamoylacetamides with aryl groups on both amide and sulfonamide groups reveal that the N-aryl substituents on acetamide are more active than those on sulfonamide. The chemoselectivity is controlled by electronic effect of the aryl group.
Annular Tautomerism of 3(5)-Disubstituted-1H-pyrazoles with Ester and Amide Groups
Authors: Kusakiewicz-Dawid Anna , Porada Monika , Dziuk Błażej , Siodłak Dawid
Published: July 2019

A series of disubstituted 1H-pyrazoles with methyl (1), amino (2), and nitro (3) groups, as well as ester (a) or amide (b) groups in positions 3 and 5 was synthesized, and annular tautomerism was investigated using X-ray, theoretical calculations, NMR, and FT-IR methods. The X-ray experiment in the crystal state showed for the compounds with methyl (1a, 1b) and amino (2b) groups the tautomer with ester or amide groups at position 3 (tautomer 3), but for those with a nitro group (3b, 4), tautomer 5. Similar results were obtained in solution by NMR NOE experiments in CDCl3, DMSO-d6, and CD3OD solvents. However, tautomer equilibrium was observed for 2b in DMSO. The FT-IR spectra in chloroform and acetonitrile showed equilibria, which can be ascribed to conformational changes of the cis/trans arrangement of the ester/amide group and pyrazole ring. Theoretical analysis using the M06-2X/6-311++G(d,p) method (in vacuo, chloroform, acetonitrile, and water) and measurement of aromaticity (NICS) showed dependence on internal hydrogen bonds, the influence of the environment, and the effect of the substituent. These factors, pyrazole aromaticity and intra- and inter-molecular interactions, seem to have a considerable influence on the choice of tautomer.
Styphnolobium japonicum (L.) Schott Fruits Increase Stress Resistance and Exert Antioxidant Properties in Caenorhabditis elegans and Mouse Models
Authors: Thabit Sara , Handoussa Heba , Roxo Mariana , Cestari de Azevedo Bruna , S.E. El Sayed Nesrine , Wink Michael
Published: July 2019

Styphnolobium japonicum (L.) Schott is a popular Asian tree widely used in traditional medicine. The current study explored the potential stress resistance and antioxidant activities of its fruits. Phytochemical profiling of the hydroalcoholic fruit extract was done via high performance liquid chromatography-photodiode array-electrospray ionization-mass/mass (HPLC-PDA-ESI-MS/MS). Twenty four phenolic constituents were tentatively identified in the extract. The Caenorhabditis elegans (C. elegans) nematode model in addition to trimethyltin (TMT)-induced neurotoxicity mouse model were used for in vivo evaluation of its antioxidant properties. The ability of the extract to enhance stress resistance was manifested through increasing survival rate by 44.7% and decreasing basal reactive oxygen species (ROS) levels by 72.3% in C. elegans. In addition, the extract increased the levels of the stress response enzyme superoxide dismutase-3 (Sod-3) by 55.5% and decreased the expression of heat shock protein-16.2 (Hsp-16.2) in nematodes, which had been challenged by juglone, by 21%. Using a mouse model, the extract significantly decreased the expression of the oxidative stress marker malondialdehyde (MDA). Furthermore, an elevation in the levels of the antioxidant marker glutathione (GSH), SOD and heme oxygenase-1 (HO-1) enzymes were observed. Our findings imply that Styphnolobium japonicum has the potential to be used in future studies focusing on diseases associated with oxidative stress.
Chiral Recognition of Carboxylate Anions by (R)-BINOL-Based Macrocyclic Receptors
Authors: Tyszka-Gumkowska Agata , Pikus Grzegorz , Jurczak Janusz
Published: July 2019

Three (R)-BINOL-based macrocyclic receptors obtained via double-amidation reaction were used for chiral recognition of four anions derived from α-hydroxy and α-amino acids. The structural factors of hosts and guests that affect chiral recognition processes were also investigated, indicating that the proper geometry of both receptor and guest molecules plays a crucial role in effective enantio-discrimination.
Multicomponent Synthesis of Polyphenols and Their In Vitro Evaluation as Potential β-Amyloid Aggregation Inhibitors
Authors: Galante Denise , Banfi Luca , Baruzzo Giulia , Basso Andrea , D’Arrigo Cristina , Lunaccio Dario , Moni Lisa , Riva Renata , Lambruschini Chiara
Published: July 2019

While plant polyphenols possess a variety of biological properties, exploration of chemical diversity around them is still problematic. Here, an example of application of the Ugi multicomponent reaction to the combinatorial assembly of artificial, yet “natural-like”, polyphenols is presented. The synthesized compounds represent a second-generation library directed to the inhibition of β-amyloid protein aggregation. Chiral enantiopure compounds, and polyphenol-β-lactam hybrids have been prepared too. The biochemical assays have highlighted the importance of the key pharmacophores in these compounds. A lead for inhibition of aggregation of truncated protein AβpE3-42 was selected.
Optimization of the Electro-Peroxone Process for Micropollutant Abatement Using Chemical Kinetic Approaches
Authors: Wang Huijiao , Su Lu , Zhu Shuai , Zhu Wei , Han Xia , Cheng Yi , Yu Gang , Wang Yujue
Published: July 2019

The electro-peroxone (E-peroxone) process is an emerging electrocatalytic ozonation process that is enabled by in situ producing hydrogen peroxide (H2O2) from cathodic oxygen reduction during ozonation. The in situ-generated H2O2 can then promote ozone (O3) transformation to hydroxyl radicals (•OH), and thus enhance the abatement of ozone-refractory pollutants compared to conventional ozonation. In this study, a chemical kinetic model was employed to simulate micropollutant abatement during the E-peroxone treatment of various water matrices (surface water, secondary wastewater effluent, and groundwater). Results show that by following the O3 and •OH exposures during the E-peroxone process, the abatement kinetics of a variety of model micropollutants could be well predicted using the model. In addition, the effect of specific ozone doses on micropollutant abatement efficiencies could be quantitatively evaluated using the model. Therefore, the chemical kinetic model can be used to reveal important information for the design and optimization of the treatment time and ozone doses of the E-peroxone process for cost-effective micropollutant abatement in water and wastewater treatment.
Novel Derivatives of Deoxycholic Acid Bearing Linear Aliphatic Diamine and Aminoalcohol Moieties and their Cyclic Analogs at the C3 Position: Synthesis and Evaluation of Their In Vitro Antitumor Potential
Authors: Markov Andrey V. , Babich Valeriya O. , Popadyuk Irina I. , Salomatina Oksana V. , Logashenko Evgeniya B. , Salakhutdinov Nariman F. , Zenkova Marina A.
Published: July 2019

A series of novel deoxycholic acid (DCA) derivatives containing aliphatic diamine and aminoalcohol or morpholine moieties at the C3 position were synthesized by 3,26-epoxide ring-opening reactions. These compounds were investigated for their cytotoxicity in four human tumor cell lines and murine macrophages and for inhibitory activity against macrophage-mediated NO synthesis in vitro. Obtained data revealed that: (i) all amine-containing substituents significantly increased the cytotoxicity of the novel compounds (IC502–10 = 1.0–36.0 μM) in comparison with DCA (IC50DCA ≥ 82.9 μM); (ii) aminoalcohol moieties were more preferable than diamine moieties due to the fact they imparted better selectivity for tumor cells of the novel derivatives; (iii) the susceptibility of tested cell lines to derivatives diminished in the following order: HuTu-80 (duodenal carcinoma) ≈ HepG2 (hepatocarcinoma) > KB-3-1 (cervical carcinoma) > RAW264.7 (macrophages) > A549 (lung carcinoma); (iv) compounds 8 and 9, bearing aminoethanol and aminopropanol moieties, respectively, exhibited high cytotoxic selectivity indexes (SIHuTu-80 = 7.9 and 8.3, respectively) and good drug-likeness parameters; (v) the novel compounds do not display anti-NO activity. Mechanistic study revealed that compound 9 induces ROS-dependent cell death by activation of intrinsic caspase-dependent apoptosis and cytodestructive autophagy in HuTu-80 cells and vitamin D receptor can be considered as its primary target.
Analysis of Chemical Composition and Assessment of Cytotoxic, Antimicrobial, and Antioxidant Activities of the Essential Oil of Meriandra dianthera Growing in Saudi Arabia
Authors: Mothana Ramzi A. , Nasr Fahd A. , Khaled Jamal M. , AL-Zharani Mohammed , Noman Omar M. , Abutaha Nael , Al-Rehaily Adnan J. , Almarfadi Omar M. , Kumar Ashok , Kurkcuoglu Mine
Published: July 2019

The essential oil of Meriandra dianthera (Konig ex Roxb.) Benth. (Synonym: Meriandra bengalensis, Lamiaceae) collected from Saudi Arabia was studied utilizing GC and GC/MS. Forty four constituents were identified, representing 96.8% of the total oil. The M. dianthera essential oil (MDEO) was characterized by a high content of oxygenated monoterpenes (76.2%). Camphor (54.3%) was the major compound in MDEO followed by 1,8-cineole (12.2%) and camphene (10.4%). Moreover, MDEO was assessed for its cytotoxic, antimicrobial, and antioxidant activities. MDEO demonstrated an interesting cytotoxic activity against all cancer cell lines with IC50 values of 83.6 to 91.2 μg/mL, especially against MCF-7 cancer cells. Using labeling with annexin VFITC and/or propidium iodide (PI) dyes and flow cytometer analysis, the apoptosis induction was quantitatively confirmed for MCF-7 cells. The MDEO exhibited a considerable antimicrobial activity against all bacterial and fungal strains with minimum inhibitory concentration (MIC)-values of 0.07 to 1.25 mg/mL. The most sensitive microbial strain was Staphylococcus aureus (MIC: 0.07 mg/mL). Minimum bactericidal concentration (MBC) or minimum fungicidal concentration (MFC) values were determined one time higher than that of MIC’s. Additionally, the MDEO revealed a strong activity for reducing β-carotene bleaching with a total antioxidant value of 72.6% and significant DPPH free radical scavenging activity (78.4%) at the concentration 1000 μg/mL.
Rheology of Polyacrylonitrile/Lignin Blends in Ionic Liquids under Melt Spinning Conditions
Authors: Jiang Jinxue , Srinivas Keerthi , Kiziltas Alper , Geda Andrew , Ahring Birgitte K.
Published: July 2019

Lignin, while economically and environmentally beneficial, has had limited success in use in reinforcing carbon fibers due to harmful chemicals used in biomass pretreatment along with the limited physical interactions between lignin and polyacrylonitrile (PAN) during the spinning process. The focus of this study is to use lignin obtained from chemical-free oxidative biomass pretreatment (WEx) for blending with PAN at melt spinning conditions to produce carbon fiber precursors. In this study, the dynamic rheology of blending PAN with biorefinery lignin obtained from the WEx process is investigated with the addition of 1-butyl-3-methylimidazolium chloride as a plasticizer to address the current barriers of developing PAN/lignin carbon fiber precursors in the melt-spinning process. Lignin was esterified using butyric anhydride to reduce its hydrophilicity and to enhance its interactions with PAN. The studies indicate that butyration of the lignin (BL) increased non-Newtonian behavior and decreased thermo-reversibility of blends. The slope of the Han plot was found to be around 1.47 for PAN at 150 °C and decreased with increasing lignin concentrations as well as temperature. However, these blends were found to have higher elasticity and solution yield stress (47.6 Pa at 20%wt BL and 190 °C) when compared to pure PAN (5.8 Pa at 190 °C). The results from this study are significant for understanding lignin–PAN interactions during melt spinning for lower-cost carbon fibers.
Topological Water Network Analysis Around Amino Acids
Authors: Choi Kwang-Eun , Chae Eunkyoung , Balupuri Anand , Yoon Hye Ree , Kang Nam Sook
Published: July 2019

Water molecules play a key role in protein stability, folding, function and ligand binding. Protein hydration has been studied using free energy perturbation algorithms. However, the study of protein hydration without free energy calculation is also an active field of research. Accordingly, topological water network (TWN) analysis has been carried out instead of free energy calculation in the present work to investigate hydration of proteins. Water networks around 20 amino acids in the aqueous solution were explored through molecular dynamics (MD) simulations. These simulation results were compared with experimental observations. Water molecules from the protein data bank structures showed TWN patterns similar to MD simulations. This work revealed that TWNs are effected by the surrounding environment. TWNs could provide valuable clues about the environment around amino acid residues in the proteins. The findings from this study could be exploited for TWN-based drug discovery and development.
Cytotoxic Polyketides from the Marine Sponge-Derived Fungus Pestalotiopsis heterocornis XWS03F09
Authors: Lei Hui , Lei Jing , Zhou Xuefeng , Hu Mei , Niu Hong , Song Can , Chen Siwei , Liu Yonghong , Zhang Dan
Published: July 2019

Four new compounds, including two new polyketides, heterocornols M and N (1, 2), and a pair of epimers, heterocornols O and P (3, 4), were isolated from the fermentation broth of the marine sponge-derived fungus Pestalotiopsis heterocornis XWS03F09, together with three known compounds (5–7). The new chemical structures were established on the basis of a spectroscopic analysis, optical rotation, experimental and calculated electronic circular dichroism (ECD). All of the compounds (1–7) were evaluated for their cytotoxic activities, and heterocornols M-P (1–4) exhibited cytotoxicities against four human cancer cell lines with IC50 values of 20.4–94.2 μM.
Characterization of Sn4P3–Carbon Composite Films for Lithium-Ion Battery Anode Fabricated by Aerosol Deposition
Authors: Moritaka Toki , Yamashita Yuh , Tojo Tomohiro , Inada Ryoji , Sakurai Yoji
Published: July 2019

We fabricated tin phosphide–carbon (Sn4P3/C) composite film by aerosol deposition (AD) and investigated its electrochemical performance for a lithium-ion battery anode. Sn4P3/C composite powders prepared by a ball milling was used as raw material and deposited onto a stainless steel substrate to form the composite film via impact consolidation. The Sn4P3/C composite film fabricated by AD showed much better electrochemical performance than the Sn4P3 film without complexing carbon. Although both films showed initial discharge (Li+ extraction) capacities of approximately 1000 mAh g−1, Sn4P3/C films retained higher reversible capacity above 700 mAh g−1 after 100 cycles of charge and discharge processes while the capacity of Sn4P3 film rapidly degraded with cycling. In addition, by controlling the potential window in galvanostatic testing, Sn4P3/C composite film retained the reversible capacity of 380 mAh g−1 even after 400 cycles. The complexed carbon works not only as a buffer to suppress the collapse of electrodes by large volume change of Sn4P3 in charge and discharge reactions but also as an electronic conduction path among the atomized active material particles in the film.
Ethynylation of Formaldehyde over Binary Cu-Based Catalysts: Study on Synergistic Effect between Cu+ Species and Acid/Base Sites
Authors: Wang Zhipeng , Ban Lijun , Meng Pingfan , Li Haitao , Zhao Yongxiang
Published: July 2019

Most studies on the Cu-based catalysts in the ethynylation of formaldehyde are merely focused on the tuning of electronic configuration and dispersion of the Cu+ species. So far, little attention has been paid to the synergy between Cu species and promoters. Herein, binary nano-CuO-MOx catalysts (M = Si, Al, and Mg) were synthesized and the effects of the promoter on the surface basicity/acidity were systematically studied as well as the ethynylation performance of the nano-CuO-based catalysts. The results show that the introduction of MgO provided a large number of basic sites, which could coordinate with the active Cu+ species and facilitate the dissociation of acetylene as HC≡Cδ− and Hδ+. The strongly nucleophilic acetylenic carbon (HC≡Cδ−) is favorable to the attack at the electropositive carbonyl Cδ+ of formaldehyde. The MgO-promoted CuO catalyst showed the highest yield of BD (94%) and the highest stability (the BD yield decreased only from 94% to 82% after eight reaction cycles). SiO2 effectively dispersed Cu species, which improved catalytic activity and stability. However, the introduction of Al2O3 resulted in a large number of acidic sites on the catalyst’s surface. This led to the polymerization of acetylene, which covered the active sites and decreased the catalyst’s activity.
Effect of Ce Doping on the Structure and Chemical Stability of Nano-α-Fe2O3
Authors: Ning Junxiang , Shi Peiyang , Jiang Maofa , Liu Chengjun , Li Xiaoliang
Published: July 2019

Ce-doped nano-α-Fe2O3 was successfully synthesized via the hydrothermal method. The properties of the prepared particles were studied by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and electrochemical methods. It was found that the Ce element can be doped into the α-Fe2O3 lattice resulting in lattice distortion, which can refine the grain and improve the crystal surface’s integrity significantly. In addition, doping of Ce element can shorten the Fe–O bond length in the α-Fe2O3 crystal, cause a blue shift of the stretching vibration band, enhance binding energy of Fe–O and the chemical stability of the α-Fe2O3 crystal.
In Vitro Toxicity of TiO2:SiO2 Nanocomposites with Different Photocatalytic Properties
Authors: Bengalli Rossella , Ortelli Simona , Blosi Magda , Costa Anna , Mantecca Paride , Fiandra Luisa
Published: July 2019

The enormous technological relevance of titanium dioxide (TiO2) nanoparticles (NPs) and the consequent concerns regarding potentially hazardous effects that exposure during production, use, and disposal can generate, encourage material scientists to develop and validate intrinsically safe design solution (safe-by-design). Under this perspective, the encapsulation in a silica dioxide (SiO2) matrix could be an effective strategy to improve TiO2 NPs safety, preserving photocatalytic and antibacterial properties. In this work, A549 cells were used to investigate the toxic effects of silica-encapsulated TiO2 having different ratios of TiO2 and SiO2 (1:1, 1:3, and 3:1). NPs were characterized by electron microscopy and dynamic light scattering, and cell viability, oxidative stress, morphological changes, and cell cycle alteration were evaluated. Resulting data demonstrated that NPs with lower content of SiO2 are able to induce cytotoxic effects, triggered by oxidative stress and resulting in cell necrosis and cell cycle alteration. The physicochemical properties of NPs are responsible for their toxicity. Particles with small size and high stability interact with pulmonary cells more effectively, and the different ratio among silica and titania plays a crucial role in the induced cytotoxicity. These results strengthen the need to take into account a safe(r)-by-design approach in the development of new nanomaterials for research and manufacturing.