bluuebunny/crossref_metadata_2025 huggingface dataset:
Wire Arc Additive Manufacturing: Review on Recent Findings and Challenges in Industrial Applications and Materials Characterization
Authors: Chaturvedi Mukti , Scutelnicu Elena , Rusu Carmen Catalina , Mistodie Luigi Renato , Mihailescu Danut , Subbiah Arungalai Vendan
Published: June 2021

Wire arc additive manufacturing (WAAM) is a fusion manufacturing process in which the heat energy of an electric arc is employed for melting the electrodes and depositing material layers for wall formation or for simultaneously cladding two materials in order to form a composite structure. This directed energy deposition-arc (DED-arc) method is advantageous and efficient as it produces large parts with structural integrity due to the high deposition rates, reduced wastage of raw material, and low consumption of energy in comparison with the conventional joining processes and other additive manufacturing technologies. These features have resulted in a constant and continuous increase in interest in this modern manufacturing technique which demands further studies to promote new industrial applications. The high demand for WAAM in aerospace, automobile, nuclear, moulds, and dies industries demonstrates compatibility and reflects comprehensiveness. This paper presents a comprehensive review on the evolution, development, and state of the art of WAAM for non-ferrous materials. Key research observations and inferences from the literature reports regarding the WAAM applications, methods employed, process parameter control, optimization and process limitations, as well as mechanical and metallurgical behavior of materials have been analyzed and synthetically discussed in this paper. Information concerning constraints and enhancements of the wire arc additive manufacturing processes to be considered in terms of wider industrial applicability is also presented in the last part of this paper.
Hypothalamic Expression of Neuropeptide Y (NPY) and Pro-OpioMelanoCortin (POMC) in Adult Male Mice Is Affected by Chronic Exposure to Endocrine Disruptors
Authors: Marraudino Marilena , Bo Elisabetta , Carlini Elisabetta , Farinetti Alice , Ponti Giovanna , Zanella Isabella , Di Lorenzo Diego , Panzica Gian Carlo , Gotti Stefano
Published: June 2021

In the arcuate nucleus, neuropeptide Y (NPY) neurons, increase food intake and decrease energy expenditure, and control the activity of pro-opiomelanocortin (POMC) neurons, that decrease food intake and increase energy expenditure. Both systems project to other hypothalamic nuclei such as the paraventricular and dorsomedial hypothalamic nuclei. Endocrine disrupting chemicals (EDCs) are environmental contaminants that alter the endocrine system causing adverse health effects in an intact organism or its progeny. We investigated the effects of long-term exposure to some EDCs on the hypothalamic NPY and POMC systems of adult male mice that had been previously demonstrated to be a target of some of these EDCs after short-term exposure. Animals were chronically fed for four months with a phytoestrogen-free diet containing two different concentrations of bisphenol A, diethylstilbestrol, tributyltin, or E2. At the end, brains were processed for NPY and POMC immunohistochemistry and quantitatively analyzed. In the arcuate and dorsomedial nuclei, both NPY and POMC immunoreactivity showed a statistically significant decrease. In the paraventricular nucleus, only the NPY system was affected, while the POMC system was not affected. Finally, in the VMH the NPY system was affected whereas no POMC immunoreactive material was observed. These results indicate that adult exposure to different EDCs may alter the hypothalamic circuits that control food intake and energy metabolism.
Stable Isotope Abundance and Fractionation in Human Diseases
Authors: Tea Illa , De Luca Arnaud , Schiphorst Anne-Marie , Grand Mathilde , Barillé-Nion Sophie , Mirallié Eric , Drui Delphine , Krempf Michel , Hankard Régis , Tcherkez Guillaume
Published: June 2021

The natural abundance of heavy stable isotopes (13C, 15N, 18O, etc.) is now of considerable importance in many research fields, including human physiology. In fact, it varies between tissues and metabolites due to isotope effects in biological processes, that is, isotope discriminations between heavy and light isotopic forms during enzyme or transporter activity. The metabolic deregulation associated with many diseases leads to alterations in metabolic fluxes, resulting in changes in isotope abundance that can be identified easily with current isotope ratio technologies. In this review, we summarize the current knowledge on changes in natural isotope composition in samples (including various tissues, hair, plasma, saliva) found in patients compared to controls, caused by human diseases. We discuss the metabolic origin of such isotope fractionations and highlight the potential of using isotopes at natural abundance for medical diagnosis and/or prognostic.
Pemafibrate Protects against Fatty Acid-Induced Nephropathy by Maintaining Renal Fatty Acid Metabolism
Authors: Aomura Daiki , Harada Makoto , Yamada Yosuke , Nakajima Takero , Hashimoto Koji , Tanaka Naoki , Kamijo Yuji
Published: June 2021

As classical agonists for peroxisomal proliferator-activated receptor alpha (PPARα), fibrates activate renal fatty acid metabolism (FAM) and provide renoprotection. However, fibrate prescription is limited in patients with kidney disease, since impaired urinary excretion of the drug causes serious adverse effects. Pemafibrate (PEM), a novel selective PPARα modulator, is mainly excreted in bile, and, thus, may be safe and effective in kidney disease patients. It remains unclear, however, whether PEM actually exhibits renoprotective properties. We investigated this issue using mice with fatty acid overload nephropathy (FAON). PEM (0.5 mg/kg body weight/day) or a vehicle was administered for 20 days to 13-week-old wild-type male mice, which were simultaneously injected with free fatty acid (FFA)-binding bovine serum albumin from day 7 to day 20 to induce FAON. All mice were sacrificed on day 20 for assessment of the renoprotective effect of PEM against FAON. PEM significantly attenuated the histological findings of tubular injury caused by FAON, increased the renal expressions of mRNA and proteins related to FAM, and decreased renal FFA content and oxidative stress. Taken together, PEM exhibits renoprotective effects through the activation and maintenance of renal FAM and represents a promising drug for kidney disease.
Challenges and Advancement of Blue III-Nitride Vertical-Cavity Surface-Emitting Lasers
Authors: Huang Chia-Yen , Hong Kuo-Bin , Huang Zhen-Ting , Hsieh Wen-Hsuan , Huang Wei-Hao , Lu Tien-Chang
Published: June 2021

Since the first demonstration of (Al, In, Ga)N-based blue vertical-cavity surface-emitting lasers (VCSELs) in 2008, the maximum output power (Pmax) and threshold current density (Jth) has been improved significantly after a decade of technology advancements. This article reviewed the key challenges for the realization of VCSELs with III-nitride materials, such as inherent polarization effects, difficulties in distributed Bragg’s reflectors (DBR) fabrication for a resonant cavity, and the anti-guiding effect due to the deposited dielectrics current aperture. The significant tensile strain between AlN and GaN hampered the intuitive cavity design with two epitaxial DBRs from arsenide-based VCSELs. Therefore, many alternative cavity structures and processing technologies were developed; for example, lattice-matched AlInN/GaN DBR, nano-porous DBR, or double dielectric DBRs via various overgrowth or film transfer processing strategies. The anti-guiding effect was overcome by integrating a fully planar or slightly convex DBR as one of the reflectors. Special designs to limit the emission polarization in a circular aperture were also summarized. Growing VCSELs on low-symmetry non-polar and semipolar planes discriminates the optical gain along different crystal orientations. A deliberately designed high-contrast grating could differentiate the reflectivity between the transverse-electric field and transverse-magnetic field, which restricts the lasing mode to be the one with the higher reflectivity. In the future, the III-nitride based VCSEL shall keep advancing in total power, applicable spectral region, and ultra-low threshold pumping density with the novel device structure design and processing technologies.
Replication Variance of African and Asian Lineage Zika Virus Strains in Different Cell Lines, Mosquitoes and Mice
Authors: Ou Tey Putita , Auerswald Heidi , In Saraden , Peng Borin , Pang Senglong , Boyer Sébastien , Choeung Rithy , Dupont-Rouzeyrol Myrielle , Dussart Philippe , Duong Veasna
Published: June 2021

Since the epidemic in 2007, studies on vector competence for Zika virus (ZIKV) have intensified, showing that the transmission efficiency varies depending on the vector population, ZIKV strain, and dose of the infectious blood meal. In this study, we aimed to investigate the replication of African and Asian ZIKV strains in vitro and in vivo in order to reveal their phenotypic differences. In addition, we investigated the vector competence of Cambodian Aedes aegypti (Ae. aegypti) mosquitoes (urban and rural) for these ZIKV strains. We observed a significantly higher pathogenicity of the African ZIKV strain in vitro (in mosquito and mammalian cells), and in vivo in both Ae. aegypti and mice. Both mosquito populations were competent to transmit ZIKV as early as 7 days p.i., depending on the population and the ZIKV strain. Ae. aegypti from rural habitats showed significant higher transmission and survival rates than those from urban. We observed the highest transmission efficiency for the African ZIKV isolate (93.3% 14 days p.i.) and for the Cambodian ZIKV isolate (80% 14 days p.i.). Overall, our results highlight the phenotypic differences of the ZIKV lineages and the potential risk of ZIKV transmission by Ae. aegypti mosquitoes. Further investigations of Cambodian mosquito species and ZIKV specific surveillance in humans is necessary in order to improve the local risk assessment.
Fermentation Strategies to Improve Soil Bio-Inoculant Production and Quality
Authors: Vassileva Maria , Malusà Eligio , Sas-Paszt Lidia , Trzcinski Pawel , Galvez Antonia , Flor-Peregrin Elena , Shilev Stefan , Canfora Loredana , Mocali Stefano , Vassilev Nikolay
Published: June 2021

The application of plant beneficial microorganisms has been widely accepted as an efficient alternative to chemical fertilizers and pesticides. Isolation and selection of efficient microorganisms, their characterization and testing in soil-plant systems are well studied. However, the production stage and formulation of the final products are not in the focus of the research, which affects the achievement of stable and consistent results in the field. Recent analysis of the field of plant beneficial microorganisms suggests a more integrated view on soil inoculants with a special emphasis on the inoculant production process, including fermentation, formulation, processes, and additives. This mini-review describes the different groups of fermentation processes and their characteristics, bearing in mind different factors, both nutritional and operational, which affect the biomass/spores yield and microbial metabolite activity. The characteristics of the final products of fermentation process optimization strategies determine further steps of development of the microbial inoculants. Submerged liquid and solid-state fermentation processes, fed-batch operations, immobilized cell systems, and production of arbuscular mycorrhiza are presented and their advantages and disadvantages are discussed. Recommendations for further development of the fermentation strategies for biofertilizer production are also considered.
Kelyphite Rims on Garnets of Contrast Parageneses in Mantle Xenoliths from the Udachnaya-East Kimberlite Pipe (Yakutia)
Authors: Pokhilenko Lyudmila
Published: June 2021

A new classification of kelyphitic rims on garnets from xenoliths of peridotitic and eclogitic parageneses of the mantle section under the Udachnaya-East kimberlite pipe (Yakutia) is presented. Five types of rims are identified: Rim1 develops between garnet and olivine/pyroxene (or rim2) and is composed of high-alumina pyroxenes, spinel, phlogopite; rim2, the coarse grain part of rim1, is located between rim1 and olivine/pyroxene, and mainly consists of phlogopite and less aluminous larger pyroxenes and spinel; rim3 develops between garnet and kimberlite, and presents with phlogopite and Fe-Ti spinel; rim4 sometimes presents instead of rim1/rim2 and consists of zoned high-Cr phlogopite with rare fine grains of chromium spinel; rim5, a “pocket” between garnet and rim1, is represented by microcrystalline aggregates of clinopyroxene, mica, spinel, calcite, and feldspar in different variations. Rims 1, 2, and 3 are typical for garnets of all studied parageneses. Rims 4 and 5 develop on high-Cr subcalcic garnets of the most depleted peridotites. Reactions of the formation of all types of rims are given in the article. Each type of kelyphite demonstrates a clear enrichment with a certain component: Rim1—MgO and alkalis; rim2—TiO2; rim3—FeO and TiO2; rim4—Cr2O3; and rim5—CaO, suggesting the multistage injection of different components by mantle fluid.
A Mottled, Non-Lithified Paleosol in Brazil: Diagnosis by Morphological and Mineralogical Features
Authors: Zinn Yuri Lopes , Miranda Camila Fernandes
Published: June 2021

The identification of paleosols is difficult when no buried horizons or lithification occur. Here, we described the identification of a possible paleosol, its characterization, and which features supported its positive diagnosis. In a construction site, a vertical cut exposed an unusual red–yellow mottling with massive structure and channels (probably faunal), in contrast with the overlying homogeneous red Oxisol with fine granular structure. A similar but more deferrified section with white–yellow mottling also occurred nearby, and both were sampled as large clods. In thin sections, many oriented clay coatings occur along channel voids, suggesting illuviation, as well as dissolving Fe nodules and Mn coatings along planar and channel voids. X-ray diffraction showed a clay dominated by kaolinite, traces of illite, and absence of gibbsite, again contrasting with the gibsitic-kaolinitic clay of the Oxisol. We confirmed the diagnosis of a Paleoultisol due to the following incompatibilities with the overlying Oxisol: (1) massive, apedal structure, and higher bulk density; (2) clay coatings indicative of illuviation as key soil-forming process; (3) low clay contents in particle-size analysis due to cementation; (4) very low organic carbon consistent with long-term inhumation; and (5) kaolinitic–illitic clay. The unusual granular microstructure of the B horizon of the Oxisol is partly derived from disintegration and desilication of the Paleoultisol.
Instrumental Photon Activation Analysis with Short-Time Irradiation for Geochemical Research
Authors: Krausová Ivana , Mizera Jiří , Řanda Zdeněk , Chvátil David , Krist Pavel
Published: June 2021

This paper introduces instrumental photon activation analysis (IPAA) utilizing short-lived products of photonuclear reactions, mainly (γ, n) and (γ, p), initiated by bremsstrahlung from the MT-25 microtron. A rapid nondestructive IPAA method for geochemical major element analysis is introduced as a tool for the basic geochemical characterization of rocks. Procedures were developed and parameters such as beam energy and irradiation-decay-counting times optimized with a representative set of geochemical reference materials, and an optimized scheme was applied in analysis of various geological samples. A complete analytical scheme combined with long-time irradiation IPAA and the possibility of utilization of photoexcitation reactions (γ, γ′) are briefly outlined.
Exploration of Polymetallic Nodules and Resource Assessment: A Case Study from the German Contract Area in the Clarion-Clipperton Zone of the Tropical Northeast Pacific
Authors: Kuhn Thomas , Rühlemann Carsten
Published: June 2021

In 2006, the BGR signed a contract with the International Seabed Authority (ISA) for the exploration of polymetallic nodules in the Clarion-Clipperton Zone of the northeast Pacific. During nine expeditions, in particular, “Area E1”, the eastern part of the contract area, with a size of ~60,000 km2, was explored in detail. Here, we outline BGR’s exploration methods and provide resource estimates for Area E1 and three sub-areas. The resource assessment is predominantly based on statistical analyses of data obtained by 12-kHz multibeam bathymetry and backscatter mapping, box core sampling and geochemical analysis of nodules. The main parameter for the assessment is the nodule abundance (kg/m2), as its coefficient of variation (CoV) over the entire eastern contract area is relatively high at 36%. In contrast, the metal contents of nodules show only minor variation, with a CoV of 8% for manganese and 8% for the sum of copper, nickel and cobalt. To estimate mineral resources for the entire Area E1, we used an artificial neural network approach with a multivariate statistical correlation between nodule abundance derived from box cores and hydro-acoustic data. The total estimated resources are 540 ± 189 million tonnes (Mt) of dry nodules, and the total estimated metal contents are 168 Mt of manganese, 7.5 Mt of nickel, 6.3 Mt of copper, 0.9 Mt of cobalt, 0.4 Mt of rare-earth elements and 0.3 Mt of molybdenum. A geostatistical resource estimate of three economically prospective areas with a total size of 4498 km2, intensively sampled by box cores, was carried out using ordinary kriging of nodule abundance and metal grades. Within these three nodule fields, 7.14 Mt of dry nodules are classified as measured mineral resources covering an area of 489 km2. Indicated mineral resources amount to 11.2 Mt, covering an area of 825 km2, and inferred mineral resources of 35.5 Mt of dry nodules were estimated for an area of 3184 km2. In total, the metal contents of the three prospective areas amount to 16.8 Mt of manganese, 0.74 Mt of nickel, 0.63 Mt of copper and 0.09 Mt of cobalt.
Mineralogy, Geochemistry, and Age Constraints on the Axinite-Bearing Gukjeon Pb–Zn Skarn Deposit in the Miryang Area, South Korea
Authors: Kim Namhoon , Koh Sang-Mo , You Byoung-Woon , Lee Bum Han
Published: June 2021

The axinite-bearing Gukjeon Pb–Zn deposit is hosted by the limestone, a member of the Jeonggaksan Formation, which, in turn, forms the part of the Jusasan subgroup of the Yucheon Group in the Gyeongsang Basin in the southeastern part of the Korean Peninsula. In this study, we attempted to interpret the spatial and temporal relationships among geologic events, including the mineralization of this deposit. We constructed a new 3D orebody model and suggested a relationship between skarn alteration and related mineralization. Mineralization timing was constrained using SHRIMP zircon age dating results combined with boron geochemistry on coeval intrusive rocks. Skarn alterations are restrictively found in several horizons of the limestone formation. The major skarn minerals are garnet (grossular), pyroxene (hedenbergite), amphibole (actinolite and ferro-actinolite), axinite (tizenite and ferro-axinite), and epidote (clinozoisite and epidote). The three stages of pre-skarn, syn-skarn, and post-skarn alteration are recognized within the deposit. The syn-skarn alteration is characterized by prograde metasomatic pyroxene and garnet, and the retrograde metasomatic amphibole, axinite, and epidote. Major skarn sulfide minerals are sphalerite, chalcopyrite, galena, and pyrite, which were predominantly precipitated during the retrograde stage and formed amphibole and axinite skarns. The skarn orebodies seem to be disc- or flat-shaped with a convex form at the central part of the orebodies. The vertical ascending and horizontal infiltration of boron-rich hydrothermal fluid probably controlled the geometry of the orebodies. Considering the whole-rock major, trace, and boron geochemical and geochronological results, the timing of Pb–Zn mineralization can be tightly constrained between the emplacement of boron-poor intrusion (fine-grained granodiorite, 82.8 Ma) and boron-rich intrusion (porphyritic andesite in Beomdori andesitic rocks, 83.8 Ma) in a back-arc basin setting. The boron for mineralization was sourced from late Cretaceous (Campanian), subduction-related magmatic rocks along the margin of the Pacific plate.
Antibacterial Activity of a Promising Antibacterial Agent: 22-(4-(2-(4-Nitrophenyl-piperazin-1-yl)-acetyl)-piperazin-1-yl)-22-deoxypleuromutilin
Authors: Zuo Xiang-Yi , Gao Hong , Gao Mei-Ling , Jin Zhen , Tang You-Zhi
Published: June 2021

A novel pleuromutilin derivative, 22-(4-(2-(4-nitrophenyl-piperazin-1-yl)-acetyl)-piperazin-1-yl)-22-deoxypleuromutilin (NPDM), was synthesized in our laboratory and proved excellent antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA). In this study, more methods were used to further study its preliminary pharmacological effect. The antibacterial efficacy and toxicity of NPDM were evaluated using tiamulin as the reference drug. The in vitro antibacterial activity study showed that NPDM is a potent bactericidal agent against MRSA that induced time-dependent growth inhibition and a concentration-dependent post-antibiotic effect (PAE). Toxicity determination showed that the cytotoxicity of NPDM was slightly higher than that of tiamulin, but the acute oral toxicity study proved that NPDM was a low-toxic compound. In an in vivo antibacterial effect study, NPDM exhibited a better therapeutic effect than tiamulin against MRSA in a mouse thigh infection model as well as a mouse systemic infection model with neutropenia. The 50% effective dose (ED50) of NPDM in a Galleria mellonella infection model was 50.53 mg/kg. The pharmacokinetic properties of NPDM were also measured, which showed that NPDM was a rapid elimination drug in mice.
In Vitro Confirmation of Siramesine as a Novel Antifungal Agent with In Silico Lead Proposals of Structurally Related Antifungals
Authors: Vlainić Josipa , Jović Ozren , Kosalec Ivan , Vugrek Oliver , Čož-Rakovac Rozelindra , Šmuc Tomislav
Published: June 2021

The limited number of medicinal products available to treat of fungal infections makes control of fungal pathogens problematic, especially since the number of fungal resistance incidents increases. Given the high costs and slow development of new antifungal treatment options, repurposing of already known compounds is one of the proposed strategies. The objective of this study was to perform in vitro experimental tests of already identified lead compounds in our previous in silico drug repurposing study, which had been conducted on the known Drugbank database using a seven-step procedure which includes machine learning and molecular docking. This study identifies siramesine as a novel antifungal agent. This novel indication was confirmed through in vitro testing using several yeast species and one mold. The results showed susceptibility of Candida species to siramesine with MIC at concentration 12.5 µg/mL, whereas other candidates had no antifungal activity. Siramesine was also effective against in vitro biofilm formation and already formed biofilm was reduced following 24 h treatment with a MBEC range of 50–62.5 µg/mL. Siramesine is involved in modulation of ergosterol biosynthesis in vitro, which indicates it is a potential target for its antifungal activity. This implicates the possibility of siramesine repurposing, especially since there are already published data about nontoxicity. Following our in vitro results, we provide additional in depth in silico analysis of siramesine and compounds structurally similar to siramesine, providing an extended lead set for further preclinical and clinical investigation, which is needed to clearly define molecular targets and to elucidate its in vivo effectiveness as well.
The Role of Essential Oils and Their Main Compounds in the Management of Cardiovascular Disease Risk Factors
Authors: Alves-Silva Jorge M. , Zuzarte Mónica , Girão Henrique , Salgueiro Lígia
Published: June 2021

Cardiovascular diseases (CVDs) are a global health burden that greatly impact patient quality of life and account for a huge number of deaths worldwide. Despite current therapies, several side effects have been reported that compromise patient adherence; thus, affecting therapeutic benefits. In this context, plant metabolites, namely volatile extracts and compounds, have emerged as promising therapeutic agents. Indeed, these compounds, in addition to having beneficial bioactivities, are generally more amenable and present less side effects, allowing better patient tolerance. The present review is an updated compilation of the studies carried out in the last 20 years on the beneficial potential of essential oils, and their compounds, against major risk factors of CVDs. Overall, these metabolites show beneficial potential through a direct effect on these risk factors, namely hypertension, dyslipidemia and diabetes, or by acting on related targets, or exerting general cellular protection. In general, monoterpenic compounds are the most studied regarding hypotensive and anti-dyslipidemic/antidiabetic properties, whereas phenylpropanoids are very effective at avoiding platelet aggregation. Despite the number of studies performed, clinical trials are sparse and several aspects related to essential oil’s features, namely volatility and chemical variability, need to be considered in order to guarantee their efficacy in a clinical setting.
Third Generation Buchwald Precatalysts with XPhos and RuPhos: Multigram Scale Synthesis, Solvent-Dependent Isomerization of XPhos Pd G3 and Quality Control by 1H- and 31P-NMR Spectroscopy
Authors: Sotnik Svitlana O. , Mishchenko Artem M. , Rusanov Eduard B. , Kozytskiy Andriy V. , Gavrilenko Konstantin S. , Ryabukhin Sergey V. , Volochnyuk Dmitriy M. , Kolotilov Sergey V.
Published: June 2021

The third generation Buchwald precatalysts Pd(ABP)(Phos)(OMs) (also known as Phos Pd G3)) with XPhos and RuPhos were prepared in multigram scale by a modified procedure (ABP = fragment of C-deprotonated 2-aminobiphenyl, XPhos = 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, RuPhos = 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl, OMs− = CH3SO3−). The 1H- and 31P-NMR spectra of the title complexes and some impurities, measured by various 1D and 2D techniques, were analyzed in detail. The solvent-dependent isomerization of Pd(ABP)(XPhos)(OMs) was studied by NMR, and the X-ray structures of two isomers were determined. The impurities in precatalysts, such as Pd(ABP)(HABP)(OMs) (HABP—neutral 2-aminobiphenyl coordinated to Pd2+ in N-monodentate mode) and PdCl2(XPhos)2, were identified and characterized by single crystal X-ray diffraction. A simple method for the quick quality control (QC) of the precatalysts, suitable for routine use, was proposed. The method was based on the assessment of the impurity content on the basis of the 1H-NMR spectra analysis.
An Easy Synthesis of Monofluorinated Derivatives of Pyrroles from β-Fluoro-β-Nitrostyrenes
Authors: Aldoshin Alexander S. , Tabolin Andrey A. , Ioffe Sema L. , Nenajdenko Valentine G.
Published: June 2021

The catalyst-free conjugate addition of pyrroles to β-Fluoro-β-nitrostyrenes was investigated. The reaction was found to proceed under solvent-free conditions to form 2-(2-Fluoro-2-nitro-1-arylethyl)-1H-pyrroles. The effectiveness of this approach was demonstrated through the preparation of a series of the target products in a quantitative yield. The kinetics of a conjugate addition of pyrrole was studied in detail to reveal the substituent effect and activation parameters of the reaction. The subsequent base-induced elimination of nitrous acid afforded a series of novel 2-(2-Fluoro-1-arylvinyl)-1H-pyrroles prepared in up to an 85% isolated yield. The two-step sequence herein proposed is an indispensable alternative to a direct reaction with elusive and unstable 1-Fluoroacetylenes.
Preparation and Characterization of Thin-Film Solar Cells with Ag/C60/MAPbI3/CZTSe/Mo/FTO Multilayered Structures
Authors: Chang Tsung-Wen , Tseng Chzu-Chiang , Chen Dave W. , Wu Gwomei , Yang Chia-Ling , Chen Lung-Chien
Published: June 2021

New solar cells with Ag/C60/MAPbI3/Cu2ZnSnSe4 (CZTSe)/Mo/FTO multilayered structures on glass substrates have been prepared and investigated in this study. The electron-transport layer, active photovoltaic layer, and hole-transport layer were made of C60, CH3NH3PbI3 (MAPbI3) perovskite, and CZTSe, respectively. The CZTSe hole-transport layers were deposited by magnetic sputtering, with the various thermal annealing temperatures at 300 °C, 400 °C, and 500 °C, and the film thickness was also varied at 50~300 nm The active photovoltaic MAPbI3 films were prepared using a two-step spin-coating method on the CZTSe hole-transport layers. It has been revealed that the crystalline structure and domain size of the MAPbI3 perovskite films could be substantially improved. Finally, n-type C60 was vacuum-evaporated to be the electronic transport layer. The 50 nm C60 thin film, in conjunction with 100 nm Ag electrode layer, provided adequate electron current transport in the multilayered structures. The solar cell current density–voltage characteristics were evaluated and compared with the thin-film microstructures. The photo-electronic power-conversion efficiency could be improved to 14.2% when the annealing temperature was 500 °C and the film thickness was 200 nm. The thin-film solar cell characteristics of open-circuit voltage, short-circuit current density, fill factor, series-resistance, and Pmax were found to be 1.07 V, 19.69 mA/cm2, 67.39%, 18.5 Ω and 1.42 mW, respectively.
Production of Siderophores by an Apple Root-Associated Streptomyces ciscaucasicus Strain GS2 Using Chemical and Biological OSMAC Approaches
Authors: Armin Reyhaneh , Zühlke Sebastian , Grunewaldt-Stöcker Gisela , Mahnkopp-Dirks Felix , Kusari Souvik
Published: June 2021

Apple Replant Disease (ARD) is a significant problem in apple orchards that causes root tissue damage, stunted plant growth, and decline in fruit quality, size, and overall yield. Dysbiosis of apple root-associated microbiome and selective richness of Streptomyces species in the rhizosphere typically concurs root impairment associated with ARD. However, possible roles of Streptomyces secondary metabolites within these observations remain unstudied. Therefore, we employed the One Strain Many Compounds (OSMAC) approach coupled to high-performance liquid chromatography-high-resolution tandem mass spectrometry (HPLC-HRMSn) to evaluate the chemical ecology of an apple root-associated Streptomycesciscaucasicus strain GS2, temporally over 14 days. The chemical OSMAC approach comprised cultivation media alterations using six different media compositions, which led to the biosynthesis of the iron-chelated siderophores, ferrioxamines. The biological OSMAC approach was concomitantly applied by dual-culture cultivation for microorganismal interactions with an endophytic Streptomyces pulveraceus strain ES16 and the pathogen Cylindrocarpon olidum. This led to the modulation of ferrioxamines produced and further triggered biosynthesis of the unchelated siderophores, desferrioxamines. The structures of the compounds were elucidated using HRMSn and by comparison with the literature. We evaluated the dynamics of siderophore production under the combined influence of chemical and biological OSMAC triggers, temporally over 3, 7, and 14 days, to discern the strain’s siderophore-mediated chemical ecology. We discuss our results based on the plausible chemical implications of S. ciscaucasicus strain GS2 in the rhizosphere.
Mechanisms of a Cyclobutane-Fused Lactone Hydrolysis in Alkaline and Acidic Conditions
Authors: Wang Zhangxia , Ma Haibo
Published: June 2021

Searching for functional polyesters with stability and degradability is important due to their potential applications in biomedical supplies, biomass fuel, and environmental protection. Recently, a cyclobutane-fused lactone (CBL) polymer was experimentally found to have superior stability and controllable degradability through hydrolysis reactions after activation by mechanical force. In order to provide a theoretical basis for developing new functional degradable polyesters, in this work, we performed a detailed quantum chemical study of the alkaline and acidic hydrolysis of CBL using dispersion-corrected density functional theory (DFT-D3) and mixed implicit/explicit solvent models. Various possible hydrolysis mechanisms were found: BAC2 and BAL2 in the alkaline condition and AAC2, AAL2, and AAL1 in the acidic condition. Our calculations indicated that CBL favors the BAC2 and AAC2 mechanisms in alkaline and acidic conditions, respectively. In addition, we found that incorporating explicit water solvent molecules is highly necessary because of their strong hydrogen-bonding with reactant/intermediate/product molecules.
Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide
Authors: Joyasawal Sipak , Ma Donghui , Doyle Michael P.
Published: June 2021

A substituted donor–acceptor cyclobutenecarboxamide is synthesized with modest enantiocontrol through a chiral copper(I) complex catalyzed [3 + 1]-cycloaddition reaction of α-acyl diphenylsulfur ylides with 3-siloxy-2-diazo-3-butenamides. With a methyl substituent on the 4-position of the 3-butenamide, the cis-vicinal-3,4-disubstituted cyclobutenecarboxamide is formed with >20:1 diastereocontrol. Donor-acceptor 3-methyl-2-siloxycyclopropenecarboxamide is rapidly formed from the reactant enoldiazoamide and undergoes catalytic ring opening to give only the Z-γ-substituted metallo-enolcarbene. Elimination from 3-siloxy-2-diazo-3-pentenamide to form the conjugated 3-siloxy-2,4-pentadienamide is competitive but minimized at low temperature.
Exploiting Protein N-Terminus for Site-Specific Bioconjugation
Authors: De Rosa Lucia , Di Stasi Rossella , Romanelli Alessandra , D’Andrea Luca Domenico
Published: June 2021

Although a plethora of chemistries have been developed to selectively decorate protein molecules, novel strategies continue to be reported with the final aim of improving selectivity and mildness of the reaction conditions, preserve protein integrity, and fulfill all the increasing requirements of the modern applications of protein conjugates. The targeting of the protein N-terminal alpha-amine group appears a convenient solution to the issue, emerging as a useful and unique reactive site universally present in each protein molecule. Herein, we provide an updated overview of the methodologies developed until today to afford the selective modification of proteins through the targeting of the N-terminal alpha-amine. Chemical and enzymatic strategies enabling the selective labeling of the protein N-terminal alpha-amine group are described.
Spruce Bark-Extracted Lignin and Tannin-Based Bioresin-Adhesives: Effect of Curing Temperatures on the Thermal Properties of the Resins
Authors: Sain Sunanda , Matsakas Leonidas , Rova Ulrika , Christakopoulos Paul , Öman Tommy , Skrifvars Mikael
Published: June 2021

In this study, formaldehyde-free bioresin adhesives were synthesised from lignin and tannin, which were obtained from softwood bark. The extraction was done via organosolv treatment and hot water extraction, respectively. A non-volatile, non-toxic aldehyde, glyoxal, was used as a substitute for formaldehyde in order to modify the chemical structure of both the lignin and tannin. The glyoxal modification reaction was confirmed by ATR–FTIR spectroscopy. Three different resin formulations were prepared using modified lignin along with the modified tannin. The thermal properties of the modified lignin, tannin, and the bioresins were assessed by DSC and TGA. When the bioresins were cured at a high temperature (200 °C) by compression moulding, they exhibited higher thermal stability as well as an enhanced degree of cross-linking compared to the low temperature-cured bioresins. The thermal properties of the resins were strongly affected by the compositions of the resins as well as the curing temperatures.
Guide to Semi-Quantitative Non-Targeted Screening Using LC/ESI/HRMS
Authors: Malm Louise , Palm Emma , Souihi Amina , Plassmann Merle , Liigand Jaanus , Kruve Anneli
Published: June 2021

Non-targeted screening (NTS) with reversed phase liquid chromatography electrospray ionization high resolution mass spectrometry (LC/ESI/HRMS) is increasingly employed as an alternative to targeted analysis; however, it is not possible to quantify all compounds found in a sample with analytical standards. As an alternative, semi-quantification strategies are, or at least should be, used to estimate the concentrations of the unknown compounds before final decision making. All steps in the analytical chain, from sample preparation to ionization conditions and data processing can influence the signals obtained, and thus the estimated concentrations. Therefore, each step needs to be considered carefully. Generally, less is more when it comes to choosing sample preparation as well as chromatographic and ionization conditions in NTS. By combining the positive and negative ionization mode, the performance of NTS can be improved, since different compounds ionize better in one or the other mode. Furthermore, NTS gives opportunities for retrospective analysis. In this tutorial, strategies for semi-quantification are described, sources potentially decreasing the signals are identified and possibilities to improve NTS are discussed. Additionally, examples of retrospective analysis are presented. Finally, we present a checklist for carrying out semi-quantitative NTS.
From Oligo(Phenyleneethynylene) Monomers to Supramolecular Helices: The Role of Intermolecular Interactions in Aggregation
Authors: Fernández Berta , Fernández Zulema , Quiñoá Emilio , Freire Félix
Published: June 2021

Supramolecular helices that arise from the self-assembly of small organic molecules via non-covalent interactions play an important role in the structure and properties of the corresponding materials. Here we study the supramolecular helical aggregation of oligo(phenyleneethynylene) monomers from a theoretical point of view, always guiding the studies with experimentally available data. In this way, by systematically increasing the number of monomer units, optimized n-mer geometries are obtained along with the corresponding absorption and circular dichroism spectra. For the geometry optimizations we use density functional theory together with the B3LYP-D3 functional and the 6–31G** basis set. For obtaining the spectra we resort to time-dependent density functional theory using the CAM-B3LYP functional and the 3–21G basis set. These combinations of density functional and basis set were selected after systematic convergence studies. The theoretical results are analyzed and compared to the experimentally available spectra, observing a good agreement.
Essential Oil Volatile Fingerprint Differentiates Croatian cv. Oblica from Other Olea europaea L. Cultivars
Authors: Popović Marijana , Jukić Špika Maja , Veršić Bratinčević Maja , Ninčević Tonka , Matešković Ana , Mandušić Marija , Rošin Jakša , Nazlić Marija , Dunkić Valerija , Vitanović Elda
Published: June 2021

Olive leaves are a highly available by-product from table olive and olive oil production. They are nowadays strongly valuable for their major bioactive compounds and their beneficial effects. To determine the differences between two Croatian domestic (Lastovka, Oblica) and two introduced (Leccino, Frantoio) cultivars, physical and chemical analysis of olive leaves were performed: surface area, color variability, total phenolic amounts, and essential oil volatile profiles were analyzed at three harvest periods. All cultivars greatly differed in surface area, with cv. Lastovka being the smallest. Color variability resulted in an overall decrease in darkness and amounts of green and yellow that could be attributed to a decrease in photosynthetic demand and chlorophyll content. The highest amount of total phenolic content occurred in the summer months, followed by a reduction until October. Essential oils volatiles were determined by GC-MS and showed great diversity not only amongst cultivars but also between harvest periods, with overall 45 compounds identified. Principal component analysis distinguished domestic cultivar Oblica from the other observed cultivars, mainly due to its essential oil volatile fingerprint. Compounds that differentiated cv. Oblica were aldehydes ((E,Z)-2,4-heptadienal, (E,E)-2,4-heptadienal, decanal), ketones ((E)-β-damascone, dihydrodehydro-β-ionone), sesquiterpenes (cyclosativene, α-copaene, α-muurolene) and saturated hydrocarbons (tetradecane, hexadecane). Essential oil volatile fingerprint attributed the highest to the biodiversity of domestic cv. Oblica through all three harvest periods.
Experimental and Theoretical Studies on Extract of Date Palm Seed as a Green Anti-Corrosion Agent in Hydrochloric Acid Solution
Authors: Mohammed Naba Jasim , Othman Norinsan Kamil , Taib Mohamad Fariz Mohamad , Samat Mohd Hazrie , Yahya Solhan
Published: June 2021

Extracts from plant materials have great potential as alternatives to inorganic corrosion inhibitors, which typically have harmful consequences. Experimental and theoretical methodologies studied the effectiveness of agricultural waste, namely, date palm seed extract as a green anti-corrosive agent in 0.5 M hydrochloric acid. Experimental results showed that immersion time and temperature are closely related to the effectivity of date palm seed as a corrosion inhibitor. The inhibition efficiency reduced from 95% to 91% at 1400 ppm when the immersion time was increased from 72 h to 168 h. The experimental results also indicated that the inhibition efficiency decreased as the temperature increased. The presence of a protective layer of organic matter was corroborated by scanning electron microscopy. The adsorption studies indicated that date palm seed obeyed Langmuir adsorption isotherm on the carbon steel surface, and Gibbs free energy values were in the range of −33.45 to −38.41 kJ·mol−1. These results suggested that the date palm seed molecules interacted with the carbon steel surface through mixture adsorption. Theoretical calculations using density functional theory showed that the capability to donate and accept electrons between the alloy surface and the date palm seed inhibitor molecules is critical for adsorption effectiveness. The HOMO and LUMO result indicated that the carboxyl (COOH) group and C=C bond were the most active sites for the electron donation-acceptance type of interaction and most auxiliary to the adsorption process over the Fe surface.
Shifted Legendre Collocation Method for the Solution of Unsteady Viscous-Ohmic Dissipative Hybrid Ferrofluid Flow over a Cylinder
Authors: Saranya Shekar , Al-Mdallal Qasem M. , Javed Shumaila
Published: June 2021

A numerical treatment for the unsteady viscous-Ohmic dissipative flow of hybrid ferrofluid over a contracting cylinder is provided in this study. The hybrid ferrofluid was prepared by mixing a 50% water (H2O) + 50% ethylene glycol (EG) base fluid with a hybrid combination of magnetite (Fe3O4) and cobalt ferrite (CoFe2O4) ferroparticles. Suitable parameters were considered for the conversion of partial differential equations (PDEs) into ordinary differential equations (ODEs). The numerical solutions were established by expanding the unknowns and employing the truncated series of shifted Legendre polynomials. We begin by collocating the transformed ODEs by setting the collocation points. These collocated equations yield a system of algebraic equations containing shifted Legendre coefficients, which can be obtained by solving this system of equations. The effect of the various influencing parameters on the velocity and temperature flow profiles were plotted graphically and discussed in detail. The effects of the parameters on the skin friction coefficient and heat transfer rates were further presented. From the discussion, we come to the understanding that Eckert number considerably decreases both the skin friction coefficient and the heat transfer rate.
Co-Encapsulation of Methylene Blue and PARP-Inhibitor into Poly(Lactic-Co-Glycolic Acid) Nanoparticles for Enhanced PDT of Cancer
Authors: Magalhães Jéssica A. , Arruda Denise C. , Baptista Maurício S. , Tada Dayane B.
Published: June 2021

The development of resistance against photodamage triggered by photodynamic therapy (PDT) is ascribed mainly to the cellular redox defenses and repair. If the tumor tissue is not promptly eliminated by the first few PDT sessions, PDT-resistance can be favored, challenging the efficacy of the treatment. Although the mechanism of PDT resistance is still unclear, in vitro assays have evidenced that it can be developed through the PARP damage-repair signaling pathway. Therefore, inhibition of poly(adenosine diphosphate (ADP)-ribose) polymerase (PARP) has the potential to increase PDT efficacy. This work reports on the synthesis of a controlled release system of a photosensitizer, methylene blue (MB) and a PARP-inhibitor, the veliparib. MB and veliparib were co-encapsulated in poly(lactic-co-glycolic acid) (PLGA) nanoparticles (VMB-NPs). A colloidal stable aqueous suspension of nanoparticles was obtained. The average hydrodynamic diameter was 90 nm and a narrow size distribution was obtained, with a polydispersity index (PDI) of 0.08. The release kinetics of MB and veliparib from VMB-NPs showed an initial burst of 8.7% and 58.3% release of the total amounts of MB and veliparib respectively, in the first 6 h, and a delayed release of up to 11.3% and 70%, in 19 days, for MB and veliparib, respectively. The VMB-NPs showed no cytotoxicity in the dark but the viability of B16F10-Nex2 cells decreased by 36% when the cells were irradiated (102 J/cm2, 660 nm) and treated with VMB-NPs containing 1.0 µM of MB and 8.3 µM of veliparib. Considering the increased photoactivity even at low MB and veliparib concentrations and the absence of cytotoxicity in dark, the co-encapsulation of MB and veliparib was shown to be a promising strategy to improve the PDT efficacy.
Development of Nanosensors Based Intelligent Packaging Systems: Food Quality and Medicine
Authors: Chelliah Ramachandran , Wei Shuai , Daliri Eric Banan-Mwine , Rubab Momna , Elahi Fazle , Yeon Su-Jung , Jo Kyoung hee , Yan Pianpian , Liu Shucheng , Oh Deog Hwan
Published: June 2021

The issue of medication noncompliance has resulted in major risks to public safety and financial loss. The new omnipresent medicine enabled by the Internet of things offers fascinating new possibilities. Additionally, an in-home healthcare station (IHHS), it is necessary to meet the rapidly increasing need for routine nursing and on-site diagnosis and prognosis. This article proposes a universal and preventive strategy to drug management based on intelligent and interactive packaging (I2Pack) and IMedBox. The controlled delamination material (CDM) seals and regulates wireless technologies in novel medicine packaging. As such, wearable biomedical sensors may capture a variety of crucial parameters via wireless communication. On-site treatment and prediction of these critical factors are made possible by high-performance architecture. The user interface is also highlighted to make surgery easier for the elderly, disabled, and patients. Land testing incorporates and validates an approach for prototyping I2Pack and iMedBox. Additionally, sustainability, increased product safety, and quality standards are crucial throughout the life sciences. To achieve these standards, intelligent packaging is also used in the food and pharmaceutical industries. These technologies will continuously monitor the quality of a product and communicate with the user. Data carriers, indications, and sensors are the three most important groups. They are not widely used at the moment, although their potential is well understood. Intelligent packaging should be used in these sectors and the functionality of the systems and the values presented in this analysis.