bluuebunny/crossref_metadata_2025 huggingface dataset:
Open Porous α + β Titanium Alloy by Liquid Metal Dealloying for Biomedical Applications
Authors: Berger Stefan Alexander , Okulov Ilya Vladimirovich
Published: October 2020

Open porous dendrite-reinforced TiMo alloy was synthesized by liquid metal dealloying of the precursor Ti47.5Mo2.5Cu50 (at.%) alloy in liquid magnesium (Mg). The porous TiMo alloy consists of α-titanium and β-titanium phases and possesses a complex microstructure. The microstructure consists of micrometer scale β-titanium dendrites surrounded by submicrometer scale α-titanium ligaments. Due to the dendrite-reinforced microstructure, the porous TiMo alloy possesses relatively high yield strength value of up to 180 MPa combined with high deformability probed under compression loading. At the same time, the elastic modulus of the porous TiMo alloy (below 10 GPa) is in the range of that found for human bone. This mechanical behavior along with the open porous structure is attractive for biomedical applications and suggests opportunities for using the porous TiMo alloy in implant applications.
Process Optimization and Formation Analysis of Friction Plug Welding of 6082 Aluminum Alloy
Authors: Zhang Zhongke , Li Xuanbai , Zhao Zaolong , Jiang Changming , Zhao Huaxia
Published: October 2020

The response surface analysis method was used to systematically study the effect of various parameters on the tensile strength of 6082 aluminum alloy friction plug welding (FPW) joints in this work. The fluidity of the joint and microstructure were observed with a metallurgical microscope. Combined with the temperature field and force analysis, the reason why the root of the joint appears as a weak zone was explained. The results showed that the degree of influence on the tensile strength of FPW joints was rotational speed > upsetting speed > welding time. The optimal FPW joint was obtained when the rotational speed was 2254 rpm, the upsetting speed was 2 mm/s, and the welding time was 25 s, so the tensile strength could reach 262.34 MPa. The microstructure of the FPW joint appeared heterogeneous. According to the different plastic metal fluidities of the joint, it could be divided into four areas. The interaction force at the friction interface was not strong at the root of the FPW joint, so the root often becomes the weak area of the FPW joint.
Separation of Permethylated O-Glycans, Free Oligosaccharides, and Glycosphingolipid-Glycans Using Porous Graphitized Carbon (PGC) Column
Authors: Cho Byeong Gwan , Peng Wenjing , Mechref Yehia
Published: October 2020

Glycosylation is one of the most common and complex post-translational modifications of proteins. However, there are other carbohydrates such as free oligosaccharides and glycosphingolipids-glycans that are associated with important biological and clinical roles. To analyze these molecules using liquid chromatography coupled with mass spectrometry (LC-MS), the permethylation approach was utilized. Although permethylation is a commonly utilized glycan derivatization technique, separation of permethylated glycans released from glycosphingolipid (GSL) by LC-MS has never been previously demonstrated. Here, a nanoflow porous graphitized carbon (PGC) column coupled with a high-resolution mass spectrometer was used to achieve isomeric separation of these permethylated glycans. We demonstrate the separation of free reducing end and reduced end O-glycans, free oligosaccharides derived from human milk, and GSL glycans derived from the MDA-MB-231BR cancer cell line using PGC-LC-MS.
Enhanced Metabolome Coverage and Evaluation of Matrix Effects by the Use of Experimental-Condition-Matched 13C-Labeled Biological Samples in Isotope-Assisted LC-HRMS Metabolomics
Authors: Ćeranić Asja , Bueschl Christoph , Doppler Maria , Parich Alexandra , Xu Kangkang , Lemmens Marc , Buerstmayr Hermann , Schuhmacher Rainer
Published: October 2020

Stable isotope-assisted approaches can improve untargeted liquid chromatography-high resolution mass spectrometry (LC-HRMS) metabolomics studies. Here, we demonstrate at the example of chemically stressed wheat that metabolome-wide internal standardization by globally 13C-labeled metabolite extract (GLMe-IS) of experimental-condition-matched biological samples can help to improve the detection of treatment-relevant metabolites and can aid in the post-acquisition assessment of putative matrix effects in samples obtained upon different treatments. For this, native extracts of toxin- and mock-treated (control) wheat ears were standardized by the addition of uniformly 13C-labeled wheat ear extracts that were cultivated under similar experimental conditions (toxin-treatment and control) and measured with LC-HRMS. The results show that 996 wheat-derived metabolites were detected with the non-condition-matched 13C-labeled metabolite extract, while another 68 were only covered by the experimental-condition-matched GLMe-IS. Additional testing is performed with the assumption that GLMe-IS enables compensation for matrix effects. Although on average no severe matrix differences between both experimental conditions were found, individual metabolites may be affected as is demonstrated by wrong decisions with respect to the classification of significantly altered metabolites. When GLMe-IS was applied to compensate for matrix effects, 272 metabolites showed significantly altered levels between treated and control samples, 42 of which would not have been classified as such without GLMe-IS.
Genetic Variability in Antioxidative and Inflammatory Pathways Modifies the Risk for PCOS and Influences Metabolic Profile of the Syndrome
Authors: Herman Rok , Jensterle Mojca , Janež Andrej , Goričar Katja , Dolžan Vita
Published: October 2020

Polycystic ovary syndrome (PCOS) is a complex endocrine and metabolic disorder of multifactorial etiopathology likely to involve the interactions between genetics and lifestyle. Chronic inflammation and oxidative stress (OS) may participate in the pathophysiology of the syndrome. The question of the extent to which OS and inflammation are causally related to the development of the syndrome and metabolic complications remains unanswered. By our knowledge, the role of the NLR family pyrin domain containing 3 (NLRP3) inflammasome as an important trigger of inflammatory pathways and NLRP3 and CARD8 polymorphisms has never been addressed in PCOS yet. We conducted a case-control study conducting of total 169 Slovenian PCOS patients and 83 healthy blood donors. They were genotyped for polymorphisms in antioxidative (SOD2 rs4880, CAT rs1001179, PON1 rs854560, and rs662) and inflammatory pathways genes (NLRP3 rs35829419, CARD8 rs2043211, TNF rs1800629, IL1B rs1143623, and rs16944, IL6 rs1800795) using competitive allele-specific polymerase chain reaction (PCR). Logistic regression and the Mann–Whitney test were used in the statistical analysis. SOD2 rs4880, CARD8 rs2043211, and IL1B rs16944 were associated with the risk of developing PCOS. Furthermore, the interactions between CARD8 rs2043211 and IL6 rs1800795 and between IL1B rs1143623 and IL6 rs1800795 also significantly affected the risk for PCOS. With regard to glucose homeostasis, CAT rs1001179, SOD2 rs4880, PON1 rs854560, NLRP3 rs35829419, and TNF rs1800629 were significantly associated with response to the glycemic load. Our data indicate that the genetic variability in the antioxidative and inflammatory pathways influences the development of PCOS and glucose homeostasis in PCOS patients.
Non-Diffractive Bessel Beams for Ultrafast Laser Scanning Platform and Proof-Of-Concept Side-Wall Polishing of Additively Manufactured Parts
Authors: Nguyen Huu Dat , Sedao Xxx , Mauclair Cyril , Bidron Guillaume , Faure Nicolas , Moreno Enrique , Colombier Jean-Philippe , Stoian Razvan
Published: October 2020

We report the potential use of non-diffractive Bessel beam for ultrafast laser processing in additive manufacturing environments, its integration into a fast scanning platform, and proof-of-concept side-wall polishing of stainless steel-based additively fabricated parts. We demonstrate two key advantages of the zeroth-order Bessel beam: the significantly long non-diffractive length for large tolerance of sample positioning and the unique self-reconstruction property for un-disrupted beam access, despite the obstruction of metallic powders in the additive manufacturing environment. The integration of Bessel beam scanning platform is constructed by finely adapting the Bessel beam into a Galvano scanner. The beam sustained its good profile within the scan field of 35 × 35 mm2. As a proof of concept, the platform showcases its advanced capacity by largely reducing the side-wall surface roughness of an additively as-fabricated workpiece from Ra 10 μm down to 1 μm. Therefore, the demonstrated Bessel–Scanner configuration possesses great potential for integrating in a hybrid additive manufacturing apparatus.
Defining Coral Bleaching as a Microbial Dysbiosis within the Coral Holobiont
Authors: Boilard Aurélie , Dubé Caroline E. , Gruet Cécile , Mercière Alexandre , Hernandez-Agreda Alejandra , Derome Nicolas
Published: October 2020

Coral microbiomes are critical to holobiont health and functioning, but the stability of host–microbial interactions is fragile, easily shifting from eubiosis to dysbiosis. The heat-induced breakdown of the symbiosis between the host and its dinoflagellate algae (that is, “bleaching”), is one of the most devastating outcomes for reef ecosystems. Yet, bleaching tolerance has been observed in some coral species. This review provides an overview of the holobiont’s diversity, explores coral thermal tolerance in relation to their associated microorganisms, discusses the hypothesis of adaptive dysbiosis as a mechanism of environmental adaptation, mentions potential solutions to mitigate bleaching, and suggests new research avenues. More specifically, we define coral bleaching as the succession of three holobiont stages, where the microbiota can (i) maintain essential functions for holobiont homeostasis during stress and/or (ii) act as a buffer to mitigate bleaching by favoring the recruitment of thermally tolerant Symbiodiniaceae species (adaptive dysbiosis), and where (iii) environmental stressors exceed the buffering capacity of both microbial and dinoflagellate partners leading to coral death.
Microbial Origin of Aquaponic Water Suppressiveness against Pythium aphanidermatum Lettuce Root Rot Disease
Authors: Stouvenakers Gilles , Massart Sébastien , Depireux Pierre , Jijakli M. Haïssam
Published: October 2020

Aquaponic systems are an integrated way to produce fish and plants together with mutual benefits. Fish provide nutrients to plants on the one side, and plant nutrients uptake allow water reuse for fish on the other side. In this kind of system, the use of phytosanitary treatments to control plant pathogens is sensitive because of the risk of toxicity for fish present in the same water loop, especially coupled aquaponics. Among plant pathogens, Pythium aphanidermatum is a most problematic microorganism due to the Oomycete’s capacity to produce mobile form of dispersion (zoospores) in the recirculated water. Therefore, this study aimed at elucidating the potential antagonistic capacity of aquaponic water against P. aphanidermatum diseases. It was shown that aquaponic water presented an inhibitory effect on P. aphanidermatum mycelial growth in in vitro conditions. The same result was observed when lettuce plants growing in aquaponic water were inoculated by the same plant pathogen. Aquaponic lettuce was then compared to lettuce grown in hydroponic water or complemented aquaponic water (aquaponic water plus mineral nutrients). The disease was suppressed in the presence of aquaponic water, contrary to lettuce grown in hydroponic water or complemented aquaponic water. Root microbiota were analyzed by 16S rDNA and ITS Illumina sequencing to determine the cause of this aquaponic suppressive action. It was determined that the diversity and the composition of the root microbiota were significantly correlated with the suppressive effect of aquaponic water. Several taxa identified by metabarcoding were suspected to be involved in this effect. Moreover, few of these microorganisms, at the genus level, are known to have an antagonistic effect against P. aphanidermatum. These innovative results indicate that aquaponic water could be an interesting and novel source of antagonistic agents adapted to control P. aphanidermatum diseases in soilless culture.
Expanding the Geographic Characterisation of Epstein–Barr Virus Variation through Gene-Based Approaches
Authors: Telford Marco , Hughes David A. , Juan David , Stoneking Mark , Navarro Arcadi , Santpere Gabriel
Published: October 2020

The Epstein–Barr Virus (EBV) infects the vast majority of human individuals worldwide (~90%) and is associated with several diseases, including different types of cancer and multiple sclerosis, which show wide variation in incidence among global geographical regions. Genetic variants in EBV genomic sequences have been used to determine the geographical structure of EBV isolates, but our understanding of EBV diversity remains highly incomplete. We generated sequences for 13 pivotal EBV genes derived from 103 healthy individuals, expanding current EBV diversity datasets with respect to both geographic coverage and number of isolates per region. These newly generated sequences were integrated with the more than 250 published EBV genomes, generating the most geographically comprehensive data set of EBV strains to date. We report remarkable variation in single-gene phylogenies that, when analysed together, show robust signals of population structure. Our results not only confirm known major global patterns of geographic variation, such as the clear separation of Asian isolates from the rest, and the intermixed relationships among African, European and Australian isolates, but yield novel phylogenetic relationships with previously unreported populations. We provide a better understanding of EBV’s population structure in South America, Africa and, by the inclusion of Turkey and Georgia, we also gain insight into EBV diversity in Western Asia, a crossroads connecting Europe, Africa and Asia. In summary, our results provide a detailed world-wide characterisation of EBV genetic clusters, their enrichment in specific geographic regions, novel inter-population relationships, and a catalogue of geographically informative EBV genetic variants.
UV-A Irradiation Increases Scytonemin Biosynthesis in Cyanobacteria Inhabiting Halites at Salar Grande, Atacama Desert
Authors: Orellana Gabriela , Gómez-Silva Benito , Urrutia Milton , Galetović Alexandra
Published: October 2020

Microbial consortia inhabiting evaporitic salt nodules at the Atacama Desert are dominated by unculturable cyanobacteria from the genus Halothece. Halite nodules provide transparency to photosynthetically active radiation and diminish photochemically damaging UV light. Atacama cyanobacteria synthesize scytonemin, a heterocyclic dimer, lipid soluble, UV-filtering pigment (in vivo absorption maximum at 370 nm) that accumulates at the extracellular sheath. Our goal was to demonstrate if UV-A irradiations modulate scytonemin biosynthesis in ground halites containing uncultured Halothece sp. cyanobacteria. Pulverized halite nodules with endolithic colonization were incubated under continuous UV-A radiation (3.6 W/m2) for 96 h, at 67% relative humidity, mimicking their natural habitat. Scytonemin content and relative transcription levels of scyB gene (a key gene in the biosynthesis of scytonemin) were evaluated by spectrophotometry and quantitative RT-PCR, respectively. After 48 h under these experimental conditions, the ratio scytonemin/chlorophyll a and the transcription of scyB gene increased to a maximal 1.7-fold value. Therefore, endolithic Halothece cyanobacteria in halites are metabolically active and UV radiation is an environmental stressor with a positive influence on scyB gene transcription and scytonemin biosynthesis. Endolithobiontic cyanobacteria in Atacama show a resilient evolutive and adaptive strategy to survive in one of the most extreme environments on Earth.
Integrated into Environmental Biofilm Chromobacterium vaccinii Survives Winter with Support of Bacterial Community
Authors: Egorova Daria A. , Voronina Olga L. , Solovyev Andrey I. , Kunda Marina S. , Aksenova Ekaterina I. , Ryzhova Natalia N. , Danilova Ksenya V. , Rykova Valentina S. , Scherbakova Anastasya A. , Semenov Andrey N. , Polyakov Nikita B. , Grumov Daniil A. , Shevlyagina Natalia V. , Dolzhikova Inna V. , Romanova Yulia M. , Gintsburg Alexander L.
Published: October 2020

Chromobacterium species are common in tropical and subtropical zones in environmental samples according to numerous studies. Here, we describe an environmental case of resident Chromobacterium vaccinii in biofilms associated with Carex spp. roots in Moscow region, Russia (warm-summer humid continental climate zone). We performed broad characterization of individual properties as well as surrounding context for better understanding of the premise of C. vaccinii survival during the winter season. Genome properties of isolated strains propose some insights into adaptation to habit and biofilm mode of life, including social cheaters carrying ΔluxR mutation. Isolated C. vaccinii differs from previously described strains in some biochemical properties and some basic characteristics like fatty acid composition as well as unique genome features. Despite potential to modulate membrane fluidity and presence of several genes responsible for cold shock response, isolated C. vaccinii did not survive during exposure to 4 °C, while in the complex biofilm sample, it was safely preserved for at least half a year in vitro at 4 °C. The surrounding bacterial community within the same biofilm with C. vaccinii represented a series of psychrophilic bacterial species, which may share resistance to low temperatures with other species within biofilm and provide C. vaccinii an opportunity to survive during the cold winter season.
Current Targets and Bioconjugation Strategies in Photodynamic Diagnosis and Therapy of Cancer
Authors: Gomez Salvador , Tsung Allan , Hu Zhiwei
Published: October 2020

Photodynamic diagnosis (PDD) and therapy (PDT) are emerging, non/minimally invasive techniques for cancer diagnosis and treatment. Both techniques require a photosensitizer and light to visualize or destroy cancer cells. However, a limitation of conventional, non-targeted PDT is poor selectivity, causing side effects. The bioconjugation of a photosensitizer to a tumor-targeting molecule, such as an antibody or a ligand peptide, is a way to improve selectivity. The bioconjugation strategy can generate a tumor-targeting photosensitizer conjugate specific for cancer cells, or ideally, for multiple tumor compartments to improve selectivity and efficacy, such as cancer stem cells and tumor neovasculature within the tumor microenvironment. If successful, such targeted photosensitizer conjugates can also be used for specific visualization and detection of cancer cells and/or tumor angiogenesis (an early event in tumorigenesis) with the hope of an early diagnosis of cancer. The purpose of this review is to summarize some current promising target molecules, e.g., tissue factor (also known as CD142), and the currently used bioconjugation strategies in PDT and PDD, with a focus on newly developed protein photosensitizers. These are genetically engineered photosensitizers, with the possibility of generating a fusion protein photosensitizer by recombinant DNA technology for both PDT and PDD without the need of chemical conjugation. We believe that providing an overview of promising targets and bioconjugation strategies will aid in driving research in this field forward towards more effective, less toxic, and non- or minimally invasive treatment and diagnosis options for cancer patients.
Evaluation of Polyhedral Oligomeric Silsesquioxane Porphyrin Derivatives on Photodynamic Therapy
Authors: Siano Paolo , Johnston Alexis , Loman-Cortes Paula , Zhin Zaneta , Vivero-Escoto Juan L.
Published: October 2020

Polyhedral oligomeric silsesquioxane (POSS) is a promising scaffold to be used as delivery system. POSS can modify the properties of photosensitizers to enhance their efficacy toward photodynamic therapy (PDT). In this work, we designed, synthesized and characterized five different POSS porphyrin (POSSPs 1–5) derivatives containing hydrophobic (1–3) and hydrophilic (4 and 5) functional groups. In general, all the POSSPs showed a better singlet oxygen quantum yield than the parent porphyrins due to the steric hindrance from the POSS unique structure. POSSPs 1 and 3 containing isobutyl groups showed better PDT performance in cancer cells at lower concentrations than POSSPs 4 and 5. However; at higher concentrations, the POSSP4 containing hydrophilic groups has an enhanced PDT efficiency as compared with the parent porphyrin. We envision that the chemical tunability of POSSs can be used as a promising option to improve the delivery and performance of photosensitizers.
Synthetic Route to Glycosyl β-1C-(phosphino)-phosphonates as Unprecedented Stable Glycosyl Diphosphate Analogs and Their Preliminary Biological Evaluation
Authors: Bosco Michaël , Paik Su-Jin , Busca Patricia , Moore Stuart E. H. , Gravier-Pelletier Christine
Published: October 2020

The synthesis of glycosyl-β-1C-(phosphino)-phosphonates is a challenge since it has not yet been described. In this paper, we report an innovative synthetic method for their preparation from Glc-, Man-, and GlcNAc- lactone derivatives. The proposed original strategy involves the addition of the corresponding δ-hexonolactones onto the dianion of (methylphosphino) phosphonate as a key step, followed by dehydration and stereoselective addition of dihydrogen on the resulting double bond. Final deprotection provides the new glycosyl diphosphate analogs in 35%, 36%, and 10% yield over 6 steps from the corresponding δ-hexonolactones. The synthetized compounds were evaluated as inhibitors of phosphatase and diphosphatase activities and found to have complex concentration-dependent activatory and inhibitory properties on alkaline phosphatase. The synthetized tools should be useful to study other enzymes such as transferases.
Evaluation of Anti-Mycobacterial Compounds in a Silkworm Infection Model with Mycobacteroides abscessus
Authors: Hosoda Kanji , Koyama Nobuhiro , Hamamoto Hiroshi , Yagi Akiho , Uchida Ryuji , Kanamoto Akihiko , Tomoda Hiroshi
Published: October 2020

Among four mycobacteria, Mycobacterium avium, M. intracellulare, M. bovis BCG and Mycobacteroides (My.) abscessus, we established a silkworm infection assay with My. abscessus. When silkworms (fifth-instar larvae, n = 5) were infected through the hemolymph with My. abscessus (7.5 × 107 CFU/larva) and bred at 37 °C, they all died around 40 h after injection. Under the conditions, clarithromycin and amikacin, clinically used antimicrobial agents, exhibited therapeutic effects in a dose-dependent manner. Furthermore, five kinds of microbial compounds, lariatin A, nosiheptide, ohmyungsamycins A and B, quinomycin and steffimycin, screened in an in vitro assay to observe anti-My. abscessus activity from 400 microbial products were evaluated in this silkworm infection assay. Lariatin A and nosiheptide exhibited therapeutic efficacy. The silkworm infection model with My. abscessus is useful to screen for therapeutically effective anti-My. abscessus antibiotics.
Quantification of Cooking Method Effect on COP Content in Meat Types Using Triple Quadrupole GC-MS/MS
Authors: Hashari Shazamawati Zam , Rahim Alina Abdul , Meng Goh Yong , Ramiah Suriya Kumari
Published: October 2020

A diet containing cholesterol is an essential component of biological function; however, cholesterol oxidation products (COPs) remain a major public health concern. This study investigated the effects of cooking methods (boiling and frying) on the production levels of COPs in processed foods. Samples, as represented by minced beef, chicken sausages, and fish fillets, were subjected to different cooking methods followed by COP extraction using a saponification method. Then, six common COPs, 5α-cholest, α-epoxy, β-epoxy, 25-HC, triol, and 7-keto, were quantified by triple quadrupole gas chromatography–mass spectrometry (GS-MS/MS). A significantly high number of COPs were detected in minced meat, of which 7-keto and triol were detected as major oxidation products, followed by chicken sausages and fish fillets (p ≤ 0.05). Compared to boiling, frying generated significantly more COPs, specifically triol (0.001–0.004 mg/kg) and 7-keto (0.001–0.200 mg/kg), in all samples. Interestingly, cholesterol level was found to be slightly (but not significantly) decreased in heat-treated samples due to oxidation during cooking, producing a higher number of COPs. Notably, the fish fillets were found to produce the fewest COPs due to the presence of a low amount of cholesterol and unsaturated fatty acids. In conclusion, adapting boiling as a way of cooking and choosing the right type of meat could serve to reduce COPs in processed foods.
Analysis of Commercial Proanthocyanidins. Part 6: Sulfitation of Flavan-3-Ols Catechin and Epicatechin, and Procyanidin B-3
Authors: Noreljaleel Anwar E.M. , Wilhelm Anke , Bonnet Susan L.
Published: October 2020

Proanthocyanidins (PACs) are natural plant-derived polymers consisting of flavan-3-ol monomers. Quebracho (Schinopsis lorentzii and balansae) heartwood and mimosa (Acacia mearnsii) bark extracts are the major industrial sources of PACs. These commercial extracts are often sulfited to reduce their viscosity and increase their solubility in water. The chemical process of sulfitation is still poorly understood regarding stereochemical influences during the reaction and during the cleavage of the interflavanyl bond of oligomers. To gain a better understanding of sulfitation, two diastereomeric flavan-3-ol monomers were sulfited under industrial conditions, and procyanidin B-3 (catechin-4α→8-catechin) were sulfited to investigate interflavanyl bond cleavage with sulfitation at C-4. Treatment of diastereomeric flavan-3-ols 2R,3S-catechin and 2R,3R-epicatechin with NaHSO3 at 100 °C in aqueous medium afforded the enantiomeric (1R,2S)- and (1S,2R)-1-(3,4-dihydroxyphenyl)-2-hydroxy-3-(2,4,6-trihydroxyphenyl)propane-1-sulfonic acid, respectively. Utilizing computational NMR PD4 calculations it was determined that the direction of stereoselective nucleophilic attack is controlled by the C-3 configuration of the flavan-3-ols catechin and epicatechin. Sulfitation of the catechin-4α→8-catechin dimer 7 (procyanidin B-3) under the same conditions led to the cleavage of the interflavanyl bond yielding the C-4 sulfonic acid substituted catechin momomer. From the heterocyclic ring coupling constants it was determined that nucleophilic attack occurs from the β-face of the dimer leading to the 2,3-trans-3,4-cis isomer as product.
Platinum Nanoparticles: Green Synthesis and Biomedical Applications
Authors: Fahmy Sherif Ashraf , Preis Eduard , Bakowsky Udo , Azzazy Hassan Mohamed El-Said
Published: October 2020

Platinum nanoparticles (PtNPs) have superior physicochemical properties and great potential in biomedical applications. Eco-friendly and economic approaches for the synthesis of PtNPs have been developed to overcome the shortcomings of the traditional physical and chemical methods. Various biogenic entities have been utilized in the green synthesis of PtNPs, including mainly plant extracts, algae, fungi bacteria, and their biomedical effects were assessed. Other biological derivatives have been used in the synthesis of PtNPs such as egg yolk, sheep milk, honey, and bovine serum albumin protein. The green approaches for the synthesis of PtNPs have reduced the reaction time, the energy required, and offered ambient conditions of fabrication. This review highlights the state-of-the-art methods used for green synthesis of PtNPs, synthesis parameters, and their reported biomedical applications.
The Role of Zinc(II) Ion in Fluorescence Tuning of Tridentate Pincers: A Review
Authors: Diana Rosita , Panunzi Barbara
Published: October 2020

Tridentate ligands are simple low-cost pincers, easy to synthetize, and able to guarantee stability to the derived complexes. On the other hand, due to its unique mix of structural and optical properties, zinc(II) ion is an excellent candidate to modulate the emission pattern as desired. The present work is an overview of selected articles about zinc(II) complexes showing a tuned fluorescence response with respect to their tridentate ligands. A classification of the tridentate pincers was carried out according to the binding donor atom groups, specifically nitrogen, oxygen, and sulfur donor atoms, and depending on the structure obtained upon coordination. Fluorescence properties of the ligands and the related complexes were compared and discussed both in solution and in the solid state, keeping an eye on possible applications.
Choline Hydrogen Dicarboxylate Ionic Liquids by X-ray Scattering, Vibrational Spectroscopy and Molecular Dynamics: H-Fumarate and H-Maleate and Their Conformations
Authors: Di Muzio Simone , Ramondo Fabio , Gontrani Lorenzo , Ferella Francesco , Nardone Michele , Benassi Paola
Published: October 2020

We explore the structure of two ionic liquids based on the choline cation and the monoanion of the maleic acid. We consider two isomers of the anion (H-maleate, the cis-isomer and H-fumarate, the trans-isomer) having different physical chemical properties. H-maleate assumes a closed structure and forms a strong intramolecular hydrogen bond whereas H-fumarate has an open structure. X-ray diffraction, infrared and Raman spectroscopy and molecular dynamics have been used to provide a reliable picture of the interactions which characterize the structure of the fluids. All calculations indicate that the choline cation prefers to connect mainly to the carboxylate group through OH⋯O interactions in both the compounds and orient the charged head N(CH3)3+ toward the negative portion of the anion. However, the different structure of the two anions affects the distribution of the ionic components in the fluid. The trans conformation of H-fumarate allows further interactions between anions through COOH and CO2− groups whereas intramolecular hydrogen bonding in H-maleate prevents this association. Our theoretical findings have been validated by comparing them with experimental X-ray data and infrared and Raman spectra.
Experimental and Theoretical Studies of a Spirostannole and Formation of a Pentaorganostannate
Authors: Ramirez y Medina Isabel-Maria , Rohdenburg Markus , Kipke Waldemar , Lork Enno , Staubitz Anne
Published: October 2020

A new spirostannole, 1,1′,3,3′-tetrakis(5-methylthiophen-2-yl)-4,4′,5,5′,6,6′,7,7′-octahydro-2,2′-spirobi[benzo[c]stannole] (4), is synthesised and the molecular structure is compared with the optimised geometry from DFT calculations. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are twice degenerated and show a small HOMO–LUMO energy gap of 3.2 eV. In addition, cyclic voltammetry measurements are conducted and three redox processes are observed. Absorption and emission spectra show maxima at λabs,max 436 nm and λem,max 533 nm, respectively. Spirostannole 4 is a strongly absorbing material, but an extremely weak emitter in solution at 295.15 K. However, when the solution is cooled from 280 to 80 K, the emission becomes visible. The reaction of spirostannole 4 with methyllithium is monitored by NMR spectroscopy at 238.15 K. The 119Sn{1H} NMR signal shifts from −36.0 (4) to −211.0 ppm, which is indicative of the formation of the lithium pentaorganostannate 5. The complex is thermally instable at 295.15 K, but insights into the molecular structure and electronic behaviour are obtained by DFT and TD-DFT calculations.
Identification of Iminium Intermediates Generation in the Metabolism of Tepotinib Using LC-MS/MS: In Silico and Practical Approaches to Bioactivation Pathway Elucidation
Authors: Abdelhameed Ali S. , Attwa Mohamed W. , Kadi Adnan A.
Published: October 2020

Tepotinib (Tepmetko™, Merck) is a potent inhibitor of c-Met (mesenchymal−epithelial transition factor). In March 2020, tepotinib (TEP) was approved for use in Japan for the treatment of patients who suffered from non-small cell lung cancers (NSCLC) harboring an MET exon 14 skipping alteration and have progressed after platinum-based therapy. Practical and in silico experiments were used to screen for the metabolic profile and reactive intermediates of TEP. Knowing the bioactive center and structural alerts in the TEP structure helped in making targeted modifications to improve its safety. First, the prediction of metabolism vulnerable sites and reactivity metabolic pathways was performed using the StarDrop WhichP450™ module and the online Xenosite reactivity predictor tool, respectively. Subsequently, in silico data were used as a guide for the in vitro practical work. Second, in vitro phase I metabolites of TEP were generated from human liver microsome (HLM) incubations. Testing for the generation of unstable reactive intermediates was performed using potassium cyanide as a capturing agent forming stable cyano adduct that can be characterized and identified using liquid chromatography tandem mass spectrometry (LC-MS/MS). Third, in silico toxicity assessment of TEP metabolites was performed, and structural modification was proposed to decrease their side effects and to validate the proposed bioactivation pathway using the DEREK software. Four TEP phase I metabolites and four cyano adducts were characterized. The reactive intermediate generation mechanism of TEP may provide an explanation of its adverse reactions. The piperidine ring is considered a structural alert for toxicity as proposed by the DEREK software and a Xenosite reactivity model, which was confirmed by practical experiments. Steric hindrance or isosteric replacement at α-carbon of the piperidine ring stop the bioactivation sequence that was confirmed using the DEREK software. More drug discovery studies can be performed using this perception permitting the design of new drugs with an increased safety profile. To our knowledge, this is the first study for the identification of in vitro phase I metabolites and reactive intermediates in addition to toxicological properties of the metabolites for TEP that will be helpful for the evaluation of TEP side effects and drug–drug interactions in TEP-treated patients.
Photooxidation of 2-(tert-Butyl)-3-Methyl-2,3,5,6,7,8-Hexahydroquinazolin-4(1H)-one, an Example of Singlet Oxygen ene Reaction
Authors: Méndez Adrian , Valdez-Camacho Jonathan Román , Escalante Jaime
Published: October 2020

Singlet oxygen ene reactions produce 2-(tert-butyl)-4a-hydroperoxy-3-methyl-2,4a, 5,6,7,8-hexahydroquinazolin-4(3H)-one quantitatively during diffusion crystallization of 2-(tert-butyl)-3-methyl-2,3,5,6,7,8-hexahydroquinazolin-4(1H)-one in n-hexane/CH2Cl2 solvent mixture. To confirm this photo-oxidation, a 1H-NMR study in CDCl3 was performed with exposure to ambient conditions (light and oxygen), with neither additional reactants nor catalysts. A theoretical study at the B3LyP/6311++G** level using the QST2 method of locating transition states suggests a two-step mechanism where the intermediate, which unexpectedly did not come from the peroxide intermediate, has a low activation energy.
In Vitro and In Vivo Biological Activity of Berberine Chloride against Uropathogenic E. coli Strains Using Galleria mellonella as a Host Model
Authors: Petronio Petronio Giulio , Cutuli Marco Alfio , Magnifico Irene , Venditti Noemi , Pietrangelo Laura , Vergalito Franca , Pane Antonella , Scapagnini Giovanni , Di Marco Roberto
Published: October 2020

Berberine is an alkaloid of the protoberberine type used in traditional oriental medicine. Its biological activities include documented antibacterial properties against a wide variety of microorganisms; nonetheless, its use against Escherichia coli strains isolated from urinary infections has not yet been widely investigated in vivo. The emergence of antimicrobial resistance requires new therapeutic approaches to ensure the continued effectiveness of antibiotics for the treatment and prevention of urinary infections. Moreover, uropathogenic Escherichia coli (UPEC) has developed several virulence factors and resistance to routine antibiotic therapy. To this end, several in vitro and in vivo tests were conducted to assess the activity of berberine on uropathogenic E. coli strains. Galleria mellonella as an infection model was employed to confirm the in vivo translatability of in vitro data on berberine activity and its influence on adhesion and invasion proprieties of E. coli on human bladder cells. In vitro pre-treatment with berberine was able to decrease the adhesive and invasive UPEC ability. In vivo treatment increased the larvae survival infected with UPEC strains and reduced the number of circulating pathogens in larvae hemolymph. These preliminary findings demonstrated the efficacy and reliability of G. mellonella as in vivo model for pre-clinical studies of natural substances.
On a Magical Mystery Tour of Green Insecticide Research: Current Issues and Challenges
Authors: Benelli Giovanni
Published: October 2020

The Editorial outlines recent research advances in green insecticide research. Particular attention is devoted to studies shedding light on the modes of action and non-target toxicity of natural substances of plant origin. Research focusing on the development of new formulations (including those relating to nano-objects) to magnify the effectiveness and stability of green insecticides in the field represents key advances. Herein, a carefully reviewed selection of cutting edge articles about green pesticide development recently published in Molecules is presented. The impact of sub-lethal doses of green insecticides on insect behavioral traits is still overlooked, representing a timely challenge for further research.
The Influence of pH Values on the Rheological, Textural and Release Properties of Carbomer Polacril® 40P-Based Dental Gel Formulation with Plant-Derived and Synthetic Active Components
Authors: Maslii Yuliia , Ruban Olena , Kasparaviciene Giedre , Kalveniene Zenona , Materiienko Anna , Ivanauskas Liudas , Mazurkeviciute Agne , Kopustinskiene Dalia M. , Bernatoniene Jurga
Published: October 2020

The physicochemical properties, especially pH value of dental medicines, have significant influence on the health of oral cavity tissues. The pH of formulations should correspond to the value of saliva pH (5.5–8.0). For carbomer-based gels, the required pH value is obtained by neutralizing them with alkaline components, which leads to their structuring (thickening). This affects the physical properties of the gel, its residence time at the application site and the rate of release of active pharmaceutical ingredient. Therefore, the main purpose of this study is to evaluate the rheological, textural, and biopharmaceutical properties of Carbomer Polacril® 40P-based dental gel depending on the pH value. Evaluation of the rheological properties of gel preparations were performed by measuring the structural viscosity of the samples as a function of pH and temperature. The textural properties of the gel were evaluated by performing tests regarding back extrusion and spreadability. Carbomer Polacril® 40P-based gels haven’t shown noticeable thixotropic behavior, and were characterized by plastic flow in the whole studied pH range. The structural viscosity at the selected average pH value hasn’t differed at storage (25 °C) and application (37 °C) temperature. Texture studies of dental gels have shown a strong correlation with rheoparameters. Their rheological behavior and textural properties haven’t changed significantly between the pH range of 5.5–6.6. The relatively narrow range of working pH values does not affect the change in the viscosity of the preparation significantly and, consequently, does not affect the release of APIs from the developed Carbomer Polacril® 40P-based dental gel.
Hybrid Boron-Carbon Chemistry
Authors: Oliva-Enrich Josep M. , Alkorta Ibon , Elguero José
Published: October 2020

The recently proved one-to-one structural equivalence between a conjugated hydrocarbon CnHm and the corresponding borane BnHm+n is applied here to hybrid systems, where each C=C double bond in the hydrocarbon is consecutively substituted by planar B(H2)B moieties from diborane(6). Quantum chemical computations with the B3LYP/cc-pVTZ method show that the structural equivalences are maintained along the substitutions, even for non-planar systems. We use as benchmark aromatic and antiaromatic (poly)cyclic conjugated hydrocarbons: cyclobutadiene, benzene, cyclooctatetraene, pentalene, benzocyclobutadiene, naphthalene and azulene. The transformation of these conjugated hydrocarbons to the corresponding boranes is analyzed from the viewpoint of geometry and electronic structure.
Botanical and Genetic Identification Followed by Investigation of Chemical Composition and Biological Activities on the Scabiosa atropurpurea L. Stem from Tunisian Flora
Authors: Hrichi Soukaina , Chaabane-Banaoues Raja , Bayar Sihem , Flamini Guido , Oulad El Majdoub Yassine , Mangraviti Domenica , Mondello Luigi , El Mzoughi Ridha , Babba Hamouda , Mighri Zine , Cacciola Francesco
Published: October 2020

Scarce information about the phenolic composition of Scabiosa atropurpurea L. is available, and no carotenoid compounds have been reported thus far. In this study the phenolic and carotenoid composition of this plant was both investigated and associated bioactivities were evaluated. Aiming to obtain extracts and volatile fractions of known medicinal plants to valorize them in the pharmaceutical or food industries, two techniques of extraction and five solvents were used to determine the biologically active compounds. Gas chromatography coupled to flame ionization and mass spectrometry and liquid chromatography coupled to photodiode array and atmospheric pressure chemical ionization/electrospray ionization mass spectrometry highlighted the presence of 15 volatiles, 19 phenolics, and 24 natural pigments in Scabiosa atropurpurea L. stem samples; among them, the most abundant were 1,8-cineole, chlorogenic acid, cynaroside, and lutein. Bioactivity was assessed by a set of in vitro tests checking for antioxidant, antibacterial, antifungal, and allelopathic (against Brassica oleracea L. and Lens culinaris Medik) effects. Scabiosa atropurpurea L. stem extracts presented a considerable antioxidant, antibacterial, and allelopathic potential, with less antifungal effectiveness. These results indicate that the volatile fractions and extracts from S. atropurpurea L. stem could be considered as a good source of bioactive agents, with possible applications in food-related, agriculture, and pharmaceutical fields. Genetic investigations showed 97% of similarity with Scabiosa tschiliensis, also called Japanese Scabiosa.
Chemical Nature of Electrode and the Switching Response of RF-Sputtered NbOx Films
Authors: Aziz Jamal , Kim Honggyun , Rehman Shania , Khan Muhammad Farooq , Kim Deok-kee
Published: October 2020

In this study, the dominant role of the top electrode is presented for Nb2O5-based devices to demonstrate either the resistive switching or threshold characteristics. These Nb2O5-based devices may exhibit different characteristics depending on the selection of electrode. The use of the inert electrode (Au) initiates resistive switching characteristics in the Au/Nb2O5/Pt device. Alternatively, threshold characteristics are induced by using reactive electrodes (W and Nb). The X-ray photoelectron spectroscopy analysis confirms the presence of oxide layers of WOy and NbOx at interfaces for W and Nb as top electrodes. However, no interface layer between the top electrode and active layer is detected in X-ray photoelectron spectroscopy for Au as the top electrode. Moreover, the dominant phase is Nb2O5 for Au and NbO2 for W and Nb. The threshold characteristics are attributed to the reduction of Nb2O5 phase to NbO2 due to the interfacial oxide layer formation between the reactive top electrode and Nb2O5. Additionally, reliability tests for both resistive switching and threshold characteristics are also performed to confirm switching stabilities.
Properties of Graphene-Related Materials Controlling the Thermal Conductivity of Their Polymer Nanocomposites
Authors: Colonna Samuele , Battegazzore Daniele , Eleuteri Matteo , Arrigo Rossella , Fina Alberto
Published: October 2020

Different types of graphene-related materials (GRM) are industrially available and have been exploited for thermal conductivity enhancement in polymers. These include materials with very different features, in terms of thickness, lateral size and composition, especially concerning the oxygen to carbon ratio and the possible presence of surface functionalization. Due to the variability of GRM properties, the differences in polymer nanocomposites preparation methods and the microstructures obtained, a large scatter of thermal conductivity performance is found in literature. However, detailed correlations between GRM-based nanocomposites features, including nanoplatelets thickness and size, defectiveness, composition and dispersion, with their thermal conductivity remain mostly undefined. In the present paper, the thermal conductivity of GRM-based polymer nanocomposites, prepared by melt polymerization of cyclic polybutylene terephtalate oligomers and exploiting 13 different GRM grades, was investigated. The selected GRM, covering a wide range of specific surface area, size and defectiveness, secure a sound basis for the understanding of the effect of GRM properties on the thermal conductivity of their relevant polymer nanocomposites. Indeed, the obtained thermal conductivity appeares to depend on the interplay between the above GRM feature. In particular, the combination of low GRM defectiveness and high filler percolation density was found to maximize the thermal conductivity of nanocomposites.
Metal Oxide Nanolayer-Decorated Epitaxial Graphene: A Gas Sensor Study
Authors: Rodner Marius , Icardi Adam , Kodu Margus , Jaaniso Raivo , Schütze Andreas , Eriksson Jens
Published: October 2020

In this manuscript, we explore the sensor properties of epitaxially grown graphene on silicon carbide decorated with nanolayers of CuO, Fe3O4, V2O5, or ZrO2. The sensor devices were investigated in regard to their response towards NH3 as a typical reducing gas and CO, C6H6, CH2O, and NO2 as gases of interest for air quality monitoring. Moreover, the impact of operating temperature, relative humidity, and additional UV irradiation as changes in the sensing environment have been explored towards their impact on sensing properties. Finally, a cross-laboratory study is presented, supporting stable sensor responses, and the final data is merged into a simplified sensor array. This study shows that sensors can be tailored not only by using different materials but also by applying different working conditions, according to the requirements of certain applications. Lastly, a combination of several different sensors into a sensor array leads to a well-performing sensor system that, with further development, could be suitable for several applications where there is no solution on the market today.