bluuebunny/crossref_metadata_2025 huggingface dataset:
Investigating the Fluid–Solid Interaction of Acid Nonionic Nanoemulsion with Carbonate Porous Media
Authors: Lucas Cláudio Regis dos Santos , Aum Yanne Katiussy Pereira Gurgel , Araújo Edson de Andrade , Castro Dantas Tereza Neuma de , Araújo Elayne Andrade , Sousa Talles Nóbrega , Aum Pedro Tupã Pandava
Published: April 2020

The subject of rock–fluid interaction is important in cases where flow through porous media is occurring. One special case is when the fluid reacts with the porous matrix. In this case, the mass transfer and reaction rate control the dissolution pattern. This article aimed to study the interaction between an acid nanoemulsion system and a carbonate porous media. Nanoemulsions were developed to retard the rock’s dissolution and to promote the formation of conductivity channels. Nanoemulsions were prepared using ALK100 (alkyl alcohol ethoxylate) and RNX110 (alkylphenol ethoxylate) (nonionic surfactants), sec-butanol (co-surfactant), xylene isomers (oil phase), and a solution of HCl (aqueous phase). The obtained systems were characterized in terms of surface tension, droplet diameter, and reactivity. X-ray fluorescence/diffraction (XRF/XRD) and X-ray microtomography (microCT) were performed on carbonate porous media samples treated with the acid systems in order to observe the effects of the fluid–rock interaction. The results showed that the acid nanoemulsion, presenting a low oil content formulation, showed the low surface tension and droplet size characteristic of nanoemulsions. It was experimentally verified that the reactivity in the nanoemulsion media was mass-transfer-retarded, and that the wormhole pattern was verified under the studied conditions.
Development of Cycloaliphatic Epoxy-POSS Nanocomposite Matrices with Enhanced Resistance to Atomic Oxygen
Authors: Rivera Lopez Mayra Y. , Lambas Javier Martin , Stacey Jonathan P. , Gamage Sachithya , Suliga Agnieszka , Viquerat Andrew , Scarpa Fabrizio , Hamerton Ian
Published: April 2020

The preparation of ultra-thin CFRP laminates, which incorporate a cycloaliphatic epoxy resin reinforced with polyhedral oligomeric silsesquioxane (POSS) reagent nanofiller, using out-of-autoclave procedure is reported. The influence of the amount of POSS within the laminate on the mechanical properties and surface roughness of the laminates is analysed before and after exposure to atomic oxygen (AO) to simulate the effects of low Earth orbit (LEO). The addition of 5 wt% POSS to the base epoxy leads to an increase in both flexural strength and modulus, but these values begin to fall as the POSS content rises, possibly due to issues with agglomeration. The addition of POSS offers improved resistance against AO degradation with the laminates containing 20 wt% POSS demonstrating the lowest erosion yield (1.67 × 10−24 cm2/atom) after the equivalent of a period of 12 months in a simulated LEO environment. Exposure to AO promotes the formation of a silicon-rich coating layer on the surface of the laminate, which in turn reduces roughness and increases stiffness, as evidenced by measurements of flexural properties and spectral data after exposure.
Glucocorticoids Influencing Wnt/β-Catenin Pathway; Multiple Sites, Heterogeneous Effects
Authors: Meszaros Katalin , Patocs Attila
Published: April 2020

Glucocorticoid hormones are vital; their accurate operation is a necessity at all ages and in all life situations. Glucocorticoids regulate diverse physiological processes and they use many signaling pathways to fulfill their effect. As the operation of these hormones affects many organs, the excess of glucocorticoids is actually detrimental to the whole human body. The endogenous glucocorticoid excess is a relatively rare condition, but a significant proportion of adult people uses glucocorticoid medication for the treatment of chronic illnesses, therefore they are exposed to the side effects of long-term glucocorticoid treatment. Our review summarizes the adverse effects of glucocorticoid excess affecting bones, adipose tissue, brain and skin, focusing on those effects which involve the Wnt/β-catenin pathway.
Binding Kinetics of Ruthenium Pyrithione Chemotherapeutic Candidates to Human Serum Proteins Studied by HPLC-ICP-MS
Authors: Marković Katarina , Milačič Radmila , Marković Stefan , Kladnik Jerneja , Turel Iztok , Ščančar Janez
Published: April 2020

The development of ruthenium-based complexes for cancer treatment requires a variety of pharmacological studies, one of them being a drug’s binding kinetics to serum proteins. In this work, speciation analysis was used to study kinetics of ruthenium-based drug candidates with human serum proteins. Two ruthenium (Ru) complexes, namely [(η6-p-cymene)Ru(1-hydroxypyridine-2(1H)-thionato)Cl] (1) and [(η6-p-cymene)Ru(1-hydroxypyridine-2(1H)-thionato)pta]PF6 (2) (where pta = 1,3,5-triaza-7-phosphaadamantane), were selected. Before a kinetics study, their stability in relevant media was confirmed by nuclear magnetic resonance (NMR). Conjoint liquid chromatography (CLC) monolithic column, assembling convective interaction media (CIM) protein G and diethylamino (DEAE) disks, was used for separation of unbound Ru species from those bound to human serum transferrin (Tf), albumin (HSA) and immunoglobulins G (IgG). Eluted proteins were monitored by UV spectrometry (278 nm), while Ru species were quantified by post-column isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). Binding kinetics of chlorido (1) and pta complex (2) to serum proteins was followed from 5 min up to 48 h after incubation with human serum. Both Ru complexes interacted mainly with HSA. Complex (1) exhibited faster and more extensive interaction with HSA than complex (2). The equilibrium concentration for complex (1) was obtained 6 h after incubation, when about 70% of compound was bound to HSA, 5% was associated with IgG, whereas 25% remained unbound. In contrast, the rate of interaction of complex (2) with HSA was much slower and less extensive and the equilibrium concentration was obtained 24 h after incubation, when about 50% of complex (2) was bound to HSA and 50% remained unbound.
N-Pyrazinoyl Substituted Amino Acids as Potential Antimycobacterial Agents—the Synthesis and Biological Evaluation of Enantiomers
Authors: Juhás Martin , Kučerová Lucie , Horáček Ondřej , Janďourek Ondřej , Kubíček Vladimír , Konečná Klára , Kučera Radim , Bárta Pavel , Janoušek Jiří , Paterová Pavla , Kuneš Jiří , Doležal Martin , Zitko Jan
Published: April 2020

Tuberculosis is an infectious disease caused by Mycobacterium tuberculosis (Mtb), each year causing millions of deaths. In this article, we present the synthesis and biological evaluations of new potential antimycobacterial compounds containing a fragment of the first-line antitubercular drug pyrazinamide (PZA), coupled with methyl or ethyl esters of selected amino acids. The antimicrobial activity was evaluated on a variety of (myco)bacterial strains, including Mtb H37Ra, M. smegmatis, M. aurum, Staphylococcus aureus, Pseudomonas aeruginosa, and fungal strains, including Candida albicans and Aspergillus flavus. Emphasis was placed on the comparison of enantiomer activities. None of the synthesized compounds showed any significant activity against fungal strains, and their antibacterial activities were also low, the best minimum inhibitory concentration (MIC) value was 31.25 µM. However, several compounds presented high activity against Mtb. Overall, higher activity was seen in derivatives containing l-amino acids. Similarly, the activity seems tied to the more lipophilic compounds. The most active derivative contained phenylglycine moiety (PC-d/l-Pgl-Me, MIC < 1.95 µg/mL). All active compounds possessed low cytotoxicity and good selectivity towards Mtb. To the best of our knowledge, this is the first study comparing the activities of the d- and l-amino acid derivatives of pyrazinamide as potential antimycobacterial compounds.
The Aza-Analogous Benzo[c]phenanthridine P8-D6 Acts as a Dual Topoisomerase I and II Poison, thus Exhibiting Potent Genotoxic Properties
Authors: Aichinger Georg , Lichtenberger Falk-Bach , Steinhauer Tamara N. , Flörkemeier Inken , Del Favero Giorgia , Clement Bernd , Marko Doris
Published: April 2020

The benzo[c]phenanthridine P8-D6 was recently found to suppress the catalytic activity of both human topoisomerase (Topo) I and II. Concomitantly, potent cytotoxic activity was observed in different human tumor cell lines, raising questions about the underlying mechanisms in vitro. In the present study, we addressed the question of whether P8-D6 acts as a so-called Topo poison, stabilizing the covalent Topo–DNA intermediate, thus inducing fatal DNA strand breaks in proliferating cells. In HT-29 colon carcinoma cells, fluorescence imaging revealed P8-D6 to be taken up by the cells and to accumulate in the perinuclear region. Confocal microscopy demonstrated that the compound is partially located inside the nuclei, thus reaching the potential target. In the “in vivo complex of enzyme” (ICE) bioassay, treatment of HT-29 cells with P8-D6 for 1 h significantly enhanced the proportion of Topo I and II covalently linked to the DNA in concentrations ≥1 µM, indicating effective dual Topo poisoning. Potentially resulting DNA damage was analyzed by single-cell gel electrophoresis (“comet assay”). Already at 1 h of incubation, significant genotoxic effects were observed in the comet assay in concentrations as low as 1 nM. Taken together, the present study demonstrates the high Topo-poisoning and genotoxic potential of P8-D6 in human tumor cells.
Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111)
Authors: Ke Changming , Lin Zijing
Published: April 2020

Dehydrogenation of H3COH and H2O are key steps of methanol steam reforming on transition metal surfaces. Oxhydryl dehydrogenation reactions of HxCOH (x = 0–3) and OH on Ni (111) were investigated by DFT calculations with the OptB88-vdW functional. The transition states were searched by the climbing image nudged elastic band method and the dimer method. The activation energies for the dehydrogenation of individual HxCOH* are 68 to 91 kJ/mol, and reduced to 12–17 kJ/mol by neighboring OH*. Bader charge analysis showed the catalysis role of OH* can be attributed to the effect of hydrogen bond (H-bond) in maintaining the charge of oxhydryl H in the reaction path. The mechanism of H-bond catalysis was further demonstrated by the study of OH* and N* assisted dehydrogenation of OH*. Due to the universality of H-bond, the H-bond catalysis shown here, is of broad implication for studies of reaction kinetics.
Induced Phases of New H-bonded Supramolecular Liquid Crystal Complexes; Mesomorphic and Geometrical Estimation
Authors: Alnoman Rua B. , Ahmed Hoda A. , Hagar Mohamed , Abu Al-Ola Khulood A. , Alrefay Bedor Sh. , Haddad Bashayer A. , Albalawi Raghad F. , Aljuhani Razan H. , Aloqebi Lama D. , Alsenani Shoaa F.
Published: April 2020

New five rings architecture of 1:1 supramolecular hydrogen bonded (H-bonded) complexes were formed between 4-(2-(pyridin-4-yl)diazenyl-3-methylphenyl 4-alkoxybenzoates and 4-n-alkoxyphenyliminobenzoic acids. Mesomorphic and optical behaviors of three systems designed complexes were investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). H-bonded interactions were confirmed via FT-IR spectroscopy. Computational calculations were carried out by density functional theory (DFT) estimation for all formed complexes. Experimental evaluations were correlated with the theoretical predictions and results revealed that, all prepared complexes possessing enantiotropic tri-mesophases with induced smectic C (SmC) and nematic temperature ranges. Moreover, DFT predicted for all formed supramolecular complexes possessing a non-linear bent geometry. Moreover, the π–π stacking of the aromatic rings plays an important role in the mesomorphic properties and thermal stabilities of observed phases. The energy changes between frontier molecular orbitals (HOMO and LUMO) and the molecular electrostatic potential (MEP) of the designed complexes were discussed and related to the experimental results.
Fatty Acid Content and Composition of the Morphological Fractions of Cistus Ladanifer L. and Its Seasonal Variation
Authors: Jerónimo Eliana , Cachucho Liliana , Soldado David , Guerreiro Olinda , Bessa Rui J. B. , Alves Susana P.
Published: April 2020

Cistus ladanifer L. is a shrub from Cistaceae family, widespread in Mediterranean countries. Fatty acids (FA) have multiple roles in plants and are involved in adaption mechanisms to environmental conditions. This work evaluated the FA content and composition of each morphological fraction of C. ladanifer (leaves, stems, flower buds, flowers and seed heads) throughout a full year. Cistus ladanifer plants were collected in southern Portugal, during four consecutive seasons (18 plants/season), and the different morphological plant fractions (leaves, stems, flower buds, flowers and seed heads) were separated. Cistus ladanifer morphological fractions showed distinct FA compositions, being possible to discriminate three groups—the leaves that showed to be dominated by saturated FA (main 20:0) and contain branched-chain FA (iso-19:0 and iso-21:0); the stems that are composed mainly by SFA (main 22:0); and the reproductive organs that showed higher contents of polyunsaturated FA (PUFA) and the 16:0 as the main SFA. The FA composition of leaves changed over seasons, with replacement of the PUFA by monounsaturated FA and branched-chain FA during hot seasons. Regarding the other C. ladanifer morphological fractions, the FA composition was more stable over seasons, suggesting that leaves are more prone to adaptations to environmental changes.
Influence of the Sample Preparation Method in Discriminating Candida spp. Using ATR-FTIR Spectroscopy
Authors: Pebotuwa Savithri , Kochan Kamila , Peleg Anton , Wood Bayden R. , Heraud Philip
Published: April 2020

Several studies have investigated the capacity of ATR-FTIR spectroscopy for fungal species discrimination. However, preparation methods vary among studies. This study aims to ascertain the effect of sample preparation on the discriminatory capacity of ATR-FTIR spectroscopy. Candida species were streaked to obtain colonies and spectra were collected from each preparation type, which included: (a) untreated colonies being directly transferred to the ATR crystal, (b) following washing and (c) following 24-h fixation in formalin. Spectra were pre-processed and principal component analysis (PCA) and K-means cluster analysis (KMC) were performed. Results showed that there was a clear discrimination between preparation types. Groups of spectra from untreated and washed isolates clustered separately due to intense protein, DNA and polysaccharide bands, whilst fixed spectra clustered separately due to intense polysaccharide bands. This signified that sample preparation had influenced the chemical composition of samples. Nevertheless, across preparation types, significant species discrimination was observed, and the polysaccharide (1200–900 cm−1) region was a common critical marker for species discrimination. However, different discriminatory marker bands were observed across preparation methods. Thus, sample preparation appears to influence the chemical composition of Candida samples; however, does not seem to significantly impact the species discrimination potential for ATR-FTIR spectroscopy.
Anthocyanin Induction by Drought Stress in the Calyx of Roselle Cultivars
Authors: Hinojosa-Gómez Jeny , San Martín-Hernández César , Heredia José B. , León-Félix Josefina , Osuna-Enciso Tomás , Muy-Rangel María D.
Published: April 2020

Abiotic factors can alter the chemical profile of crops and the number of compounds they contain. In this study, the anthocyanin and anthocyanidin contents, determined by ultra-performance liquid chromatography (UPLC-MS/MS), and the colour attributes of the calyces of three cultivars of Hibiscus sabdariffa subjected to three water stress regimes during the stage of physiological maturity were investigated. The total anthocyanin content in calyx increased relative to the control content under a 65% moisture irrigation regime. Among the cultivars, UAN16-2 showed the greatest increases in the contents of cyanidin, delphinidin 3-O-glucoside, cyanidin 3-O-glucoside, and cyanidin 3-O-sambubioside. The content of cyanidin 3-O-sambubioside showed the greatest increase, increasing by 55% relative to the control level. The contents of these compounds are correlated with colour attributes such as luminosity. Water stress under the 33% moisture condition during plant development led to decreased anthocyanin contents in all of the roselle cultivars.
Solubility, Hansen Solubility Parameters and Thermodynamic Behavior of Emtricitabine in Various (Polyethylene Glycol-400 + Water) Mixtures: Computational Modeling and Thermodynamics
Authors: Shakeel Faiyaz , Haq Nazrul , Alsarra Ibrahim A. , Alshehri Sultan
Published: April 2020

This study was aimed to find out the solubility, thermodynamic behavior, Hansen solubility parameters and molecular interactions of an antiviral drug emtricitabine (ECT) in various “[polyethylene glycol-400 (PEG-400) + water]” mixtures. The solubility of ECT in mole fraction was determined at “T = 298.2 to 318.2 K” and “p = 0.1 MPa” using an isothermal method. The experimental solubilities of ECT in mole fraction were validated and correlated using various computational models which includes “Van’t Hoff, Apelblat, Yalkowsky-Roseman, Jouyban-Acree and Jouyban-Acree-Van’t Hoff models”. All the models performed well in terms of model correlation. The solubility of ECT was increased with the raise in temperature in all “PEG-400 + water” mixtures studied. The highest and lowest solubility values of ECT were found in pure PEG-400 (1.45 × 10−1) at “T = 318.2 K” and pure water (7.95 × 10−3) at “T = 298.2 K”, respectively. The quantitative values of activity coefficients indicated higher interactions at molecular level in ECT and PEG-400 combination compared with ECT and water combination. “Apparent thermodynamic analysis” showed an “endothermic and entropy-driven dissolution” of ECT in all “PEG-400 + water” combinations studied. The solvation nature of ECT was found an “enthalpy-driven” in each “PEG-400 + water” mixture studied.
Effect of Cornstalk Biochar Immobilized Bacteria on Ammonia Reduction in Laying Hen Manure Composting
Authors: Zhang Huaidan , Marchant-Forde Jeremy N. , Zhang Xinyi , Wang Yan
Published: April 2020

NH3 emission has become one of the key factors for aerobic composting of animal manure. It has been reported that adding microbial agents during aerobic composting can reduce NH3 emissions. However, environmental factors have a considerable influence on the activity and stability of the microbial agent. Therefore, this study used cornstalk biochar as carriers to find out the better biological immobilization method to examine the mitigation ability and mechanism of NH3 production from laying hen manure composting. The results from different immobilized methods showed that NH3 was reduced by 12.43%, 5.53%, 14.57%, and 22.61% in the cornstalk biochar group, free load bacteria group, mixed load bacteria group, and separate load bacteria group, respectively. Under the simulated composting condition, NH3 production was 46.52, 38.14, 39.08, and 30.81 g in the treatment of the control, mixed bacteria, cornstalk biochar, and cornstalk biochar separate load immobilized mixed bacteria, respectively. The cornstalk biochar separate load immobilized mixed bacteria treatment significantly reduced NH3 emission compared with the other treatments (p < 0.05). Compared with the control, adding cornstalk biochar immobilized mixed bacteria significantly decreased the electrical conductivity, water-soluble carbon, total nitrogen loss, and concentration of ammonium nitrogen (p < 0.05), and significantly increased the seed germination rate, total number of microorganisms, and relative abundance of lactic acid bacteria throughout the composting process (p < 0.05). Therefore, the reason for the low NH3 emission might be due not only to the adsorption of the cornstalk biochar but also because of the role of complex bacteria, which increases the relative abundance of lactic acid bacteria and promotes the acid production of lactic acid bacteria to reduce NH3 emissions. This result revealed the potential of using biological immobilization technology to reduce NH3 emissions during laying hen manure composting.
Himalayan Nettle Girardinia diversifolia as a Candidate Ingredient for Pharmaceutical and Nutraceutical Applications—Phytochemical Analysis and In Vitro Bioassays
Authors: Sharan Shrestha Shyam , Sut Stefania , Ferrarese Irene , Barbon Di Marco Serena , Zengin Gokhan , De Franco Michele , Pant Deepak Raj , Mahomoodally Mohamad Fawzi , Ferri Nicola , Biancorosso Noemi , Maggi Filippo , Dall Acqua Stefano , Rajbhandary Sangeeta
Published: April 2020

Girardinia diversifolia, also known as Himalayan nettle, is a perennial herb used in Nepal to make fiber as well as in traditional medicine for the treatment of several diseases. To date, phytochemical studies and biological assays on this plant are scarce. Thus, in the present work, the G. diversifolia extracts have been evaluated for their potential pharmaceutical, cosmetic and nutraceutical uses. For this purpose, detailed phytochemical analyses were performed, evidencing the presence of phytosterols, fatty acids, carotenoids, polyphenols and saponins. The most abundant secondary metabolites were β- and γ-sitosterol (11 and 9% dw, respectively), and trans syringin (0.5 mg/g) was the most abundant phenolic. Fatty acids with an abundant portion of unsaturated derivatives (linoleic and linolenic acid at 22.0 and 9.7 mg/g respectively), vitamin C (2.9 mg/g) and vitamin B2 (0.12 mg/g) were also present. The antioxidant activity was moderate while a significant ability to inhibit acetylcholinesterase (AChE), butyrilcholinesterase (BuChE), tyrosinase, α-amylase and α-glucosidase was observed. A cytotoxic effect was observed on human ovarian, pancreatic and hepatic cancer cell lines. The effect in hepatocarcinoma cells was associated to a downregulation of the low-density lipoprotein receptor (LDLR), a pivotal regulator of cellular cholesterol homeostasis. These data show the potential usefulness of this species for possible applications in pharmaceuticals, nutraceuticals and cosmetics.
Reprogrammable Permanent Shape Memory Materials Based on Reversibly Crosslinked Epoxy/PCL Blends
Authors: Razquin Iker , Iregui Alvaro , Orduna Lidia , Martin Loli , González Alba , Irusta Lourdes
Published: April 2020

Epoxy/Polycaprolactone (PCL) blends cured with a conventional diamine (4,4′-diaminodiphenylmethane, DDM) and with different amounts of a disulfide containing diamine (4, 4´-dithioaniline, DSS) were prepared through melting. The curing process was studied by FTIR and differential scanning calorimetry (DSC) and the mechanical behavior of the networks was studied by DMA. The shape memory properties and the recyclability of the materials were also analyzed. All blends showed a very high curing degree and temperature activated shape memory effect, related to the glass transition of the epoxy resin. The PCL plasticized the mixture, allowing tailoring of the epoxy glass transition. In addition, in the blends cured with DSS, as a consequence of the disulfide exchange reaction, the permanent shape could be erased and a new shape could be reprogrammed. Using this strategy, reprogrammable permanent shape memory materials were obtained.
Lapatinib, Nilotinib and Lomitapide Inhibit Haemozoin Formation in Malaria Parasites
Authors: de Sousa Ana Carolina C. , Maepa Keletso , Combrinck Jill M. , Egan Timothy J.
Published: April 2020

With the continued loss of antimalarials to resistance, drug repositioning may have a role in maximising efficiency and accelerating the discovery of new antimalarial drugs. Bayesian statistics was previously used as a tool to virtually screen USFDA approved drugs for predicted β-haematin (synthetic haemozoin) inhibition and in vitro antimalarial activity. Here, we report the experimental evaluation of nine of the highest ranked drugs, confirming the accuracy of the model by showing an overall 93% hit rate. Lapatinib, nilotinib, and lomitapide showed the best activity for inhibition of β-haematin formation and parasite growth and were found to inhibit haemozoin formation in the parasite, providing mechanistic insights into their mode of antimalarial action. We then screened the USFDA approved drugs for binding to the β-haematin crystal, applying a docking method in order to evaluate its performance. The docking method correctly identified imatinib, lapatinib, nilotinib, and lomitapide. Experimental evaluation of 22 of the highest ranked purchasable drugs showed a 24% hit rate. Lapatinib and nilotinib were chosen as templates for shape and electrostatic similarity screening for lead hopping using the in-stock ChemDiv compound catalogue. The actives were novel structures worthy of future investigation. This study presents a comparison of different in silico methods to identify new haemozoin-inhibiting chemotherapeutic alternatives for malaria that proved to be useful in different ways when taking into consideration their strengths and limitations.
Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines
Authors: Modec Barbara , Podjed Nina , Lah Nina
Published: April 2020

Copper(II) acetate has reacted in methanol with quinaldinic acid (quinoline-2-carboxylic acid) to form [Cu(quin)2(CH3OH)]∙CH3OH (1) (quin− = an anionic form of the acid) with quinaldinates bound in a bidentate chelating manner. In the air, complex 1 gives off methanol and binds water. The conversion was monitored by IR spectroscopy. The aqua complex has shown a facile substitution chemistry with alicyclic secondary amines, pyrrolidine (pyro), and morpholine (morph). trans-[Cu(quin)2(pyro)2] (2) and trans-[Cu(quin)2(morph)2] (4) were obtained in good yields. The morpholine system has produced a by-product, trans-[Cu(en)2(H2O)2](morphCOO)2 (5) (morphCOO− = morphylcarbamate), a result of the copper(II) quinaldinate reaction with ethylenediamine (en), an inherent impurity in morpholine, and the amine reaction with carbon dioxide. (pyroH)[Cu(quin)2Cl] (3) forms on the recrystallization of [Cu(quin)2(pyro)2] from dichloromethane, confirming a reaction between amine and the solvent. Similarly, a homologous amine, piperidine (pipe), and dichloromethane produced (pipeH)[Cu(quin)2Cl] (11). The piperidine system has afforded both mono- and bis-amine complexes, [Cu(quin)2(pipe)] (6) and trans-[Cu(quin)2(pipe)2] (7). The latter also exists in solvated forms, [Cu(quin)2(pipe)2]∙CH3CN (8) and [Cu(quin)2(pipe)2]∙CH3CH2CN (9). Interestingly, only the piperidine system has experienced a reduction of copper(II). The involvement of amine in the reduction was undoubtedly confirmed by identification of a polycyclic piperidine compound 10, 6,13-di(piperidin-1-yl)dodecahydro-2H,6H-7,14-methanodipyrido[1,2-a:1′,2′-e][1,5]diazocine.
Antagonism of Histamine H3 receptors Alleviates Pentylenetetrazole-Induced Kindling and Associated Memory Deficits by Mitigating Oxidative Stress, Central Neurotransmitters, and c-Fos Protein Expression in Rats
Authors: Alachkar Alaa , Azimullah Sheikh , Lotfy Mohamed , Adeghate Ernest , Ojha Shreesh K. , Beiram Rami , Łażewska Dorota , Kieć-Kononowicz Katarzyna , Sadek Bassem
Published: April 2020

Histamine H3 receptors (H3Rs) are involved in several neuropsychiatric diseases including epilepsy. Therefore, the effects of H3R antagonist E177 (5 and 10 mg/kg, intraperitoneal (i.p.)) were evaluated on the course of kindling development, kindling-induced memory deficit, oxidative stress levels (glutathione (GSH), malondialdehyde (MDA), catalase (CAT), and superoxide dismutase (SOD)), various brain neurotransmitters (histamine (HA), acetylcholine (ACh), γ-aminobutyric acid (GABA)), and glutamate (GLU), acetylcholine esterase (AChE) activity, and c-Fos protein expression in pentylenetetrazole (PTZ, 40 mg/kg) kindled rats. E177 (5 and 10 mg/kg, i.p.) significantly decreased seizure score, increased step-through latency (STL) time in inhibitory avoidance paradigm, and decreased transfer latency time (TLT) in elevated plus maze (all P < 0.05). Moreover, E177 mitigated oxidative stress by significantly increasing GSH, CAT, and SOD, and decreasing the abnormal level of MDA (all P < 0.05). Furthermore, E177 attenuated elevated levels of hippocampal AChE, GLU, and c-Fos protein expression, whereas the decreased hippocampal levels of HA and ACh were modulated in PTZ-kindled animals (all P < 0.05). The findings suggest the potential of H3R antagonist E177 as adjuvant to antiepileptic drugs with an added advantage of preventing cognitive impairment, highlighting the H3Rs as a potential target for the therapeutic management of epilepsy with accompanied memory deficits.
Electrocatalytic Assisted Performance Enhancement for the Na-S Battery in Nitrogen-Doped Carbon Nanospheres Loaded with Fe
Authors: Zhu Jianhui , Abdelkader Amr , Demko Denisa , Deng Libo , Zhang Peixin , He Tingshu , Wang Yanyi , Huang Licong
Published: April 2020

Room temperature sodium-sulfur batteries have been considered to be potential candidates for future energy storage devices because of their low cost, abundance, and high performance. The sluggish sulfur reaction and the “shuttle effect” are among the main problems that hinder the commercial utilization of room temperature sodium-sulfur batteries. In this study, the performance of a hybrid that was based on nitrogen (N)-doped carbon nanospheres loaded with a meagre amount of Fe ions (0.14 at.%) was investigated in the sodium-sulfur battery. The Fe ions accelerated the conversion of polysulfides and provided a stronger interaction with soluble polysulfides. The Fe-carbon nanospheres hybrid delivered a reversible capacity of 359 mAh·g−1 at a current density of 0.1 A·g−1 and retained a capacity of 180 mAh·g−1 at 1 A·g−1, after 200 cycles. These results, combined with the excellent rate performance, suggest that Fe ions, even at low loading, are able to improve the electrocatalytic effect of carbon nanostructures significantly. In addition to Na-S batteries, the new hybrid is anticipated to be a strong candidate for other energy storage and conversion applications such as other metal-sulfur batteries and metal-air batteries.
In Situ Assessment of Intrinsic Strength of X-I⋯OA-Type Halogen Bonds in Molecular Crystals with Periodic Local Vibrational Mode Theory
Authors: Tao Yunwen , Qiu Yue , Zou Wenli , Nanayakkara Sadisha , Yannacone Seth , Kraka Elfi
Published: April 2020

Periodic local vibrational modes were calculated with the rev-vdW-DF2 density functional to quantify the intrinsic strength of the X-I⋯OA-type halogen bonding (X = I or Cl; OA: carbonyl, ether and N-oxide groups) in 32 model systems originating from 20 molecular crystals. We found that the halogen bonding between the donor dihalogen X-I and the wide collection of acceptor molecules OA features considerable variations of the local stretching force constants (0.1–0.8 mdyn/Å) for I⋯O halogen bonds, demonstrating its powerful tunability in bond strength. Strong correlations between bond length and local stretching force constant were observed in crystals for both the donor X-I bonds and I⋯O halogen bonds, extending for the first time the generalized Badger’s rule to crystals. It is demonstrated that the halogen atom X controlling the electrostatic attraction between the σ -hole on atom I and the acceptor atom O dominates the intrinsic strength of I⋯O halogen bonds. Different oxygen-containing acceptor molecules OA and even subtle changes induced by substituents can tweak the n → σ ∗ (X-I) charge transfer character, which is the second important factor determining the I⋯O bond strength. In addition, the presence of the second halogen bond with atom X of the donor X-I bond in crystals can substantially weaken the target I⋯O halogen bond. In summary, this study performing the in situ measurement of halogen bonding strength in crystalline structures demonstrates the vast potential of the periodic local vibrational mode theory for characterizing and understanding non-covalent interactions in materials.
A New Family of Iron(II)-Cyclopentadienyl Compounds Shows Strong Activity against Colorectal and Triple Negative Breast Cancer Cells
Authors: Pilon Adhan , Brás Ana Rita , Côrte-Real Leonor , Avecilla Fernando , Costa Paulo J. , Preto Ana , Garcia M. Helena , Valente Andreia
Published: April 2020

A family of compounds with the general formula [Fe(η5-C5H5)(CO)(PPh3)(NCR)]+ has been synthesized (NCR = benzonitrile (1); 4-hydroxybenzonitrile (2); 4-hydroxymethylbenzonitrile (3); 4-aminobenzonitrile (4); 4-bromobenzonitrile (5); and, 4-chlorocinnamonitrile (6)). All of the compounds were obtained in good yields and were completely characterized by standard spectroscopic and analytical techniques. Compounds 1, 4, and 5 crystallize in the monoclinc P21/c space group and packing is determined by short contacts between the phosphane phenyl rings and cyclopentadienyl (compounds 1 and 4) or π-π lateral interactions between the benzonitrile molecules (complex 5). DFT and TD-DFT calculations were performed to help in the interpretation of the experimental UV-Vis. data and assign the electronic transitions. Cytotoxicity studies in MDA-MB-231 breast and SW480 colorectal cancer-derived cell lines showed IC50 values at a low micromolar range for all of the compounds in both cell lines. The determination of the selectivity index for colorectal cells (SW480 vs. NCM460, a normal colon-derived cell line) indicates that the compounds have some inherent selectivity. Further studies on the SW480 cell line demonstrated that the compounds induce cell death by apoptosis, inhibit proliferation by inhibiting the formation of colonies, and affect the actin-cytoskeleton of the cells. These results are not observed for the hydroxylated compounds 2 and 3, where an alternative mode of action might be present. Overall, the results indicate that the substituent at the nitrile-based ligand is associated to the biological activity of the compounds.
Novel Polycondensed Partly Saturated β-Carbolines Including Ferrocene Derivatives: Synthesis, DFT-Supported Structural Analysis, Mechanism of Some Diastereoselective Transformations and a Preliminary Study of their In Vitro Antiproliferative Effects
Authors: Fodor Kinga Judit , Hutai Dániel , Jernei Tamás , Takács Angéla , Szász Zsófia , Sulyok-Eiler Máté , Harmat Veronika , Oláh Szabó Rita , Schlosser Gitta , Hudecz Ferenc , Kőhidai László , Csámpai Antal
Published: April 2020

Use of a Pictet-Spengler reaction of tryptamine and l-tryptophan methyl ester and subsequent reduction of the nitro group followed by further cyclocondensation with aryl aldehydes and formyl–substituted carboxylic acids, including ferrocene-based components, furnished a series of diastereomeric 6-aryl-substituted 5,6,8,9,14,14b-hexahydroindolo[2′,3′:3,4]pyrido[1-c]-quinazolines and 5,5b,17,18-tetrahydroindolo[2′,3′:3,4]pyrido[1,2-c]isoindolo[2,1-a]quinazolin-11-(15bH)-ones with the elements of central-, planar and conformational chirality. The relative configuration and the conformations of the novel polycyclic indole derivatives were determined by 1H- and 13C-NMR methods supplemented by comparative DFT analysis of the possible diastereomers. The structure of one of the pentacyclic methyl esters with defined absolute configuration “S” was also confirmed by single crystal X-ray diffraction measurement. Accounting for the characteristic substituent-dependent diastereoselective formation of the products multistep mechanisms were proposed on the basis of the results of DFT modeling. Preliminary in vitro cytotoxic assays of the products revealed moderate-to-significant antiproliferative effects against PANC-1-, COLO-205-, A-2058 and EBC-1 cell lines that proved to be highly dependent on the stereostructure and on the substitution pattern of the pending aryl substituent.
Role of the Neutrophil in the Pathogenesis of Advanced Cancer and Impaired Responsiveness to Therapy
Authors: Rapoport Bernardo L. , Steel Helen C. , Theron Annette J. , Smit Teresa , Anderson Ronald
Published: April 2020

Notwithstanding the well-recognized involvement of chronic neutrophilic inflammation in the initiation phase of many types of epithelial cancers, a growing body of evidence has also implicated these cells in the pathogenesis of the later phases of cancer development, specifically progression and spread. In this setting, established tumors have a propensity to induce myelopoiesis and to recruit neutrophils to the tumor microenvironment (TME), where these cells undergo reprogramming and transitioning to myeloid-derived suppressor cells (MDSCs) with a pro-tumorigenic phenotype. In the TME, these MDSCs, via the production of a broad range of mediators, not only attenuate the anti-tumor activity of tumor-infiltrating lymphocytes, but also exclude these cells from the TME. Realization of the pro-tumorigenic activities of MDSCs of neutrophilic origin has resulted in the development of a range of adjunctive strategies targeting the recruitment of these cells and/or the harmful activities of their mediators of immunosuppression. Most of these are in the pre-clinical or very early clinical stages of evaluation. Notable exceptions, however, are several pharmacologic, allosteric inhibitors of neutrophil/MDSC CXCR1/2 receptors. These agents have entered late-stage clinical assessment as adjuncts to either chemotherapy or inhibitory immune checkpoint-targeted therapy in patients with various types of advanced malignancy. The current review updates the origins and identities of MDSCs of neutrophilic origin and their spectrum of immunosuppressive mediators, as well as current and pipeline MDSC-targeted strategies as potential adjuncts to cancer therapies. These sections are preceded by a consideration of the carcinogenic potential of neutrophils.
Chlorosubstituted Copper Phthalocyanines: Spectral Study and Structure of Thin Films
Authors: Sukhikh Alexandr , Bonegardt Dmitry , Klyamer Darya , Krasnov Pavel , Basova Tamara
Published: April 2020

In this work, the tetra-, octa- and hexadecachloro-substituted copper phthalocyanines CuPcClx (where x can equal 4, 8 or 16) were investigated by the methods of vibrational (IR and Raman) spectroscopy and X-ray diffraction. The assignment of the most intense bands, both in IR and Raman spectra, was carried out on the basis of DFT calculations. The structure of a CuPcCl4 single crystal grown by sublimation in vacuum was refined for the first time. The effect of chloro-substitution on the structure of CuPcClx thin films deposited in a vacuum onto a glass substrate at 50 and 200 °C was studied. It was shown that CuPcCl4 formed polycrystalline films with the preferential orientation of the (100) crystallographic plane of crystallites parallel to the substrate surface when deposited on a substrate at 50 °C. Introduction of more Cl-substituents into the phthalocyanine macrocycle leads to the formation of amorphous films on the substrates at 50 °C. At the elevated substrate temperature, the growth of polycrystalline disordered films was observed for all three copper phthalocyanines.
Flame Retardant-Functionalized Cotton Cellulose Using Phosphonate-Based Ionic Liquids
Authors: Al Hokayem Karen , El Hage Roland , Svecova Lenka , Otazaghine Belkacem , Le Moigne Nicolas , Sonnier Rodolphe
Published: April 2020

Cellulose from cotton fibers was functionalized through a dissolution–regeneration process with phosphonate-based ionic liquids (ILs): 1,3-dimethylimidazolium methylphosphonate [DIMIM][(MeO)(H)PO2] and 1-ethyl-3-methylimidazolium methylphoshonate [EMIM][(MeO)(H)PO2]. The chemical modification of cellulose occurred through a transesterification reaction between the methyl phosphonate function of ILs and the primary alcohol functions of cellulose. The resulting cellulose structure and the amount of grafted phosphorus were then investigated by X-ray diffraction, ICP-AES, and ¹³C and ³¹P NMR spectroscopy. Depending on the IL type and initial cotton / IL ratio in the solution, regenerated cellulose contained up to 4.5% of phosphorus. The rheological behavior of cotton cellulose/ILs solutions and the microscale fire performances of modified cellulose were studied in order to ultimately prepare flame retardant cellulosic materials. Significant improvement in the flame retardancy of regenerated cellulose was obtained with a reduction of THR values down to about 5–6 kJ/g and an increase of char up to about 35 wt%.
Walnut Oil Prevents Scopolamine-Induced Memory Dysfunction in a Mouse Model
Authors: Liao Jianqiao , Nai Yifan , Feng Li , Chen Yimeng , Li Mei , Xu Huaide
Published: April 2020

For thousands of years, it has been widely believed that walnut is a kind of nut that has benefits for the human body. Walnut oil, accounting for about 70% of walnut, mainly consists of polyunsaturated fatty acids. To investigate the effect of walnut oil on memory impairment in mice, scopolamine (3 mg/kg body weight/d) was used to establish the animal model during Morris Water Maze (MWM) tests. Walnut oil was administrated orally at 10 mL/kg body weight/d for 8 consecutive weeks. The results showed that walnut oil treatment ameliorated the behavior of the memory-impaired mice in the MWM test. Additionally, walnut oil obviously inhibited acetylcholinesterase activity (1.26 ± 0.12 U/mg prot) (p = 0.013) and increased choline acetyltransferase activity (129.75 ± 6.76 U/mg tissue wet weight) in the brains of scopolamine-treated mice (p = 0.024), suggesting that walnut oil could prevent cholinergic function damage in mice brains. Furthermore, walnut oil remarkably prevented the decrease in total superoxide dismutase activity (93.30 ± 5.50 U/mg prot) (p = 0.006) and glutathione content (110.45 ± 17.70 mg/g prot) (p = 0.047) and the increase of malondialdehyde content (13.79 ± 0.96 nmol/mg prot) (p = 0.001) in the brain of scopolamine-treated mice, indicating that walnut oil could inhibit oxidative stress in the brain of mice. Furthermore, walnut oil prevented histological changes of neurons in hippocampal CA1 and CA3 regions induced by scopolamine. These findings indicate that walnut oil could prevent memory impairment in mice, which might be a potential way for the prevention of memory dysfunctions.
The Sorption Performance of Cetyl Trimethyl Ammonium Bromide-Capped La0.9Sr0.1FeO3 Perovskite for Organic Pollutants from Industrial Processes
Authors: Ali Shimaa M. , Eskandrani Areej A.
Published: April 2020

La0.9Sr0.1FeO3 perovskite, prepared by the microwave-assisted method, was capped with cetyl trimethyl ammonium bromide (CTAB) cationic surfactant, and applied as a sorbent for the removal of the anionic Congo red (CR) dye from aqueous solutions. X-ray diffraction (XRD) patterns showed that the perovskite structure was not affected by capping; however, the particle size increased. There was a hipsochromic shift in the value of λmax of the CR absorption spectrum in the presence of CTAB, which indicated the formation of an oppositely charged dye–surfactant complex. The adsorption efficiency of CTAB-capped La0.9Sr0.1FeO3 was independent of the pH of the solution—equilibrium was reached after a few minutes. The value of the maximum adsorption capacity, qm, was 151.52 mg·g−1, which was 10-times higher than that of the pure perovskite. The proposed sorbent maintained its excellent sorption ability in the presence of the sample matrix; therefore, it can be regenerated and reused with unchanged performance.
Lead-Free BNT–BT0.08/CoFe2O4 Core–Shell Nanostructures with Potential Multifunctional Applications
Authors: Cernea Marin , Radu Roxana , Amorín Harvey , Greculeasa Simona Gabriela , Vasile Bogdan Stefan , Surdu Vasile Adrian , Ganea Paul , Trusca Roxana , Hattab Marwa , Galassi Carmen
Published: April 2020

Herein we report on novel multiferroic core–shell nanostructures of cobalt ferrite (CoFe2O4)–bismuth, sodium titanate doped with barium titanate (BNT–BT0.08), prepared by a two–step wet chemical procedure, using the sol–gel technique. The fraction of CoFe2O4 was varied from 1:0.5 to 1:1.5 = BNT–BT0.08/CoFe2O4 (molar ratio). X–ray diffraction confirmed the presence of both the spinel CoFe2O4 and the perovskite Bi0.5Na0.5TiO3 phases. Scanning electron microscopy analysis indicated that the diameter of the core–shell nanoparticles was between 15 and 40 nm. Transmission electron microscopy data showed two–phase composite nanostructures consisting of a BNT–BT0.08 core surrounded by a CoFe2O4 shell with an average thickness of 4–7 nm. Cole-Cole plots reveal the presence of grains and grain boundary effects in the BNT–BT0.08/CoFe2O4 composite. Moreover, the values of the dc conductivity were found to increase with the amount of CoFe2O4 semiconductive phase. Both X-ray photoelectron spectroscopy (XPS) and Mössbauer measurements have shown no change in the valence of the Fe3+, Co2+, Bi3+ and Ti4+ cations. This study provides a detailed insight into the magnetoelectric coupling of the multiferroic BNT–BT0.08/CoFe2O4 core–shell composite potentially suitable for magnetoelectric applications.
Vaccinium macrocarpon (Cranberry)-Based Dietary Supplements: Variation in Mass Uniformity, Proanthocyanidin Dosage and Anthocyanin Profile Demonstrates Quality Control Standard Needed
Authors: Mannino Giuseppe , Di Stefano Vita , Lauria Antonino , Pitonzo Rosa , Gentile Carla
Published: April 2020

Vaccinium macrocarpon (syn. American Cranberry) is employed in dietary supplements (DS) with the aim to improve urinary tract well-being. This property is linked to the antiadhesion-activity of proanthocyanidins (PACs) against uropathogenic-bacteria. However, the current European legislation has been criticized for being weak and ineffective. Indeed, recent scientific works report mislabeled, contaminated, and adulterated supplements containing dangerous or unknown compounds, or sold at toxic doses. In this work, we analysed 24 DS that claim to contain cranberry, and to have a specific dosage of PACs. Our tests included the control of the good manufacturing practice according to the European Pharmacopoeia, and the verification of the claimed dosage of PACs. Moreover, in order to confirm the real presence of cranberry in DS, chemical fingerprinting via HPLC-UV/Vis-MS/MS was employed. Our results showed that 17 DS did not comply with the uniformity test of dosage forms, and only five contained cranberry. Finally, 16 DS claimed an incorrect amount of PACs. These data suggest that several cranberry-based DS are present in the European market with insufficient quality controls. Considering that often DS are self-prescribed by consumer relying on their claim, the data obtained in this work should encourage more controls and stricter rules.
HPLC-Based Analysis of Impurities in Sapropterin Branded and Generic Tablets
Authors: Scudellaro Emanuela , Tartaglione Luciana , Varriale Fabio , Dell’Aversano Carmela , Taglialatela-Scafati Orazio
Published: April 2020

This work was aimed at the definition of a chromatographic method able to separate and quantify impurities present in sapropterin-containing drugs during an accelerated stability study. The chromatographic method was applied to the orphan drug Kuvan® and to its corresponding generic sapropterin Dipharma (Diterin®), both of which are approved for the treatment of hyperphenylalaninemia-induced symptoms. The two products tested had a similar manufacture date and both had an approved stability shelf-life of three years. Samples were analyzed by HPLC at T = 0 and after six months of storage at 40 °C and 75% relative humidity. Identification of the impurities was supported by a detailed mass spectrometry and MS/MS profile. The analysis demonstrated an overall higher stability for the Diterin® formulation, which was related to a lower increase of some impurities compared to Kuvan®.