bluuebunny/crossref_metadata_2025 huggingface dataset:
Combination of Plasma Electrolytic Processing and Mechanical Polishing for Single-Crystal 4H-SiC
Authors: Ma Gaoling , Li Shujuan , Liu Xu , Yin Xincheng , Jia Zhen , Liu Feilong
Published: May 2021

Single-crystal 4H-SiC is a typical third-generation semiconductor power-device material because of its excellent electronic and thermal properties. A novel polishing technique that combines plasma electrolytic processing and mechanical polishing (PEP-MP) was proposed in order to polish single-crystal 4H-SiC surfaces effectively. In the PEP-MP process, the single-crystal 4H-SiC surface is modified into a soft oxide layer, which is mainly made of SiO2 and a small amount of silicon oxycarbide by plasma electrolytic processing. Then, the modified oxide layer is easily removed by soft abrasives such as CeO2, whose hardness is much lower than that of single-crystal 4H-SiC. Finally a scratch-free and damage-free surface can be obtained. The hardness of the single-crystal 4H-SiC surface is greatly decreased from 2891.03 to 72.61 HV after plasma electrolytic processing. By scanning electron microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS) observation, the plasma electrolytic processing behaviors of single-crystal 4H-SiC are investigated. The scanning white light interferometer (SWLI) images of 4H-SiC surface processed by PEP-MP for 30 s shows that an ultra-smooth surface is obtained and the surface roughness decreased from Sz 607 nm, Ra 64.5 nm to Sz 60.1 nm, Ra 8.1 nm and the material removal rate (MRR) of PEP-MP is about 21.8 μm/h.
Recent Progress on Plant-Inspired Soft Robotics with Hydrogel Building Blocks: Fabrication, Actuation and Application
Authors: Xu Zhenyu , Zhou Yongsen , Zhang Baoping , Zhang Chao , Wang Jianfeng , Wang Zuankai
Published: May 2021

Millions of years’ evolution has imparted life on earth with excellent environment adaptability. Of particular interest to scientists are some plants capable of macroscopically and reversibly altering their morphological and mechanical properties in response to external stimuli from the surrounding environment. These intriguing natural phenomena and underlying actuation mechanisms have provided important design guidance and principles for man-made soft robotic systems. Constructing bio-inspired soft robotic systems with effective actuation requires the efficient supply of mechanical energy generated from external inputs, such as temperature, light, and electricity. By combining bio-inspired designs with stimuli-responsive materials, various intelligent soft robotic systems that demonstrate promising and exciting results have been developed. As one of the building materials for soft robotics, hydrogels are gaining increasing attention owing to their advantageous properties, such as ultra-tunable modulus, high compliance, varying stimuli-responsiveness, good biocompatibility, and high transparency. In this review article, we summarize the recent progress on plant-inspired soft robotics assembled by stimuli-responsive hydrogels with a particular focus on their actuation mechanisms, fabrication, and application. Meanwhile, some critical challenges and problems associated with current hydrogel-based soft robotics are briefly introduced, and possible solutions are proposed. We expect that this review would provide elementary tutorial guidelines to audiences who are interested in the study on nature-inspired soft robotics, especially hydrogel-based intelligent soft robotic systems.
12/111phiA Prophage Domestication Is Associated with Autoaggregation and Increased Ability to Produce Biofilm in Streptococcus agalactiae
Authors: Renard Adélaïde , Diene Seydina M. , Courtier-Martinez Luka , Gaillard Julien Burlaud , Gbaguidi-Haore Houssein , Mereghetti Laurent , Quentin Roland , Francois Patrice , Van Der Mee-Marquet Nathalie
Published: May 2021

CC17 Streptococcus agalactiae carrying group-A prophages is increasingly responsible for neonatal infections. To investigate the impact of the genetic features of a group-A prophage, we first conducted an in silico analysis of the genome of 12/111phiA, a group-A prophage carried by a strain responsible for a bloodstream infection in a parturient. This revealed a Restriction Modification system, suggesting a prophage maintenance strategy and five ORFs of interest for the host and encoding a type II toxin antitoxin system RelB/YafQ, an endonuclease, an S-adenosylmethionine synthetase MetK, and an StrP-like adhesin. Using the WT strain cured from 12/111phiA and constructing deleted mutants for the ORFs of interest, and their complemented mutants, we demonstrated an impact of prophage features on growth characteristics, cell morphology and biofilm formation. Our findings argue in favor of 12/111phiA domestication by the host and a role of prophage features in cell autoaggregation, glycocalyx and biofilm formation. We suggest that lysogeny may promote GBS adaptation to the acid environment of the vagina, consequently colonizing and infecting neonates.
Environmental Conditions Modulate the Transcriptomic Response of Both Caulobacter crescentus Morphotypes to Cu Stress
Authors: Maertens Laurens , Cherry Pauline , Tilquin Françoise , Van Houdt Rob , Matroule Jean-Yves
Published: May 2021

Bacteria encounter elevated copper (Cu) concentrations in multiple environments, varying from mining wastes to antimicrobial applications of copper. As the role of the environment in the bacterial response to Cu ion exposure remains elusive, we used a tagRNA-seq approach to elucidate the disparate responses of two morphotypes of Caulobacter crescentus NA1000 to moderate Cu stress in a complex rich (PYE) medium and a defined poor (M2G) medium. The transcriptome was more responsive in M2G, where we observed an extensive oxidative stress response and reconfiguration of the proteome, as well as the induction of metal resistance clusters. In PYE, little evidence was found for an oxidative stress response, but several transport systems were differentially expressed, and an increased need for histidine was apparent. These results show that the Cu stress response is strongly dependent on the cellular environment. In addition, induction of the extracytoplasmic function sigma factor SigF and its regulon was shared by the Cu stress responses in both media, and its central role was confirmed by the phenotypic screening of a sigF::Tn5 mutant. In both media, stalked cells were more responsive to Cu stress than swarmer cells, and a stronger basal expression of several cell protection systems was noted, indicating that the swarmer cell is inherently more Cu resistant. Our approach also allowed for detecting several new transcription start sites, putatively indicating small regulatory RNAs, and additional levels of Cu-responsive regulation.
Extensive Comparative Genomic Analysis of Enterococcus faecalis and Enterococcus faecium Reveals a Direct Association between the Absence of CRISPR–Cas Systems, the Presence of Anti-Endonuclease (ardA) and the Acquisition of Vancomycin Resistance in E. faecium
Authors: Mlaga Kodjovi D. , Garcia Vincent , Colson Philippe , Ruimy Raymond , Rolain Jean-Marc , Diene Seydina M.
Published: May 2021

Here, we performed a comparative genomic analysis of all available genomes of E. faecalis (n = 1591) and E. faecium (n = 1981) and investigated the association between the presence or absence of CRISPR-Cas systems, endonuclease/anti-endonuclease systems and the acquisition of antimicrobial resistance, especially vancomycin resistance genes. Most of the analysed Enterococci were isolated from humans and less than 14% of them were from foods and animals. We analysed and detected CRISPR–Cas systems in 75.36% of E. faecalis genomes and only 4.89% of E. faecium genomes with a significant difference (p-value < 10−5). We found a negative correlation between the number of CRISPR–Cas systems and genome size (r = −0.397, p-value < 10−5) and a positive correlation between the genome %GC content and the number of CRISPR–Cas systems (r = 0.215, p-value < 10−5). Our findings showed that the presence of the anti-endonuclease ardA gene may explain the decrease in the number of CRISPR–Cas systems in E. faecium, known to deactivate the endonucleases’ protective activities and enable the E. faecium genome to be versatile in acquiring mobile genetic elements, including carriers of antimicrobial resistance genes, especially vanB. Most importantly, we observed that there was a direct association between the absence of CRISPR–Cas, the presence of the anti-CRISPR ardA gene and the acquisition of vancomycin resistance genes.
Phylogenetic Tracking of LA-MRSA ST398 Intra-Farm Transmission among Animals, Humans and the Environment on German Dairy Farms
Authors: Lienen Tobias , Schnitt Arne , Cuny Christiane , Maurischat Sven , Tenhagen Bernd-Alois
Published: May 2021

Methicillin-resistant Staphylococcus aureus (MRSA) are a major threat to human and animal health, causing difficult-to-treat infections. The aim of our study was to evaluate the intra-farm transmission of livestock-associated (LA) MRSA sequence type (ST) 398 isolates on German dairy farms. A total of 115 LA-MRSA ST398 isolates originating from animals, humans and the environment of six dairy farms were analyzed by whole-genome sequencing and core genome multilocus sequence typing. Phylogenetic clusters of high allelic similarity were detected on all dairy farms, suggesting a MRSA transmission across the different niches. On one farm, closely related isolates from quarter milk samples (QMS), suckers of calf feeders and nasal cavities of calves indicate that MRSA may be transferred by feeding contaminated milk to calves. Detection of related MRSA isolates in QMS and teat cups (4/6 farms) or QMS and human samples (3/4 farms) pointed out a transmission of MRSA between cows during the milking process and a potential zoonotic risk. In conclusion, LA-MRSA ST398 isolates may spread between animals, humans and the environment on dairy farms. Milking time hygiene and other internal biosecurity measures on farms and pre-treatment of milk before feeding it to calves may reduce the risk of MRSA transmission.
Composition of Prokaryotic and Eukaryotic Microbial Communities in Waters around the Florida Reef Tract
Authors: Laas Peeter , Ugarelli Kelly , Absten Michael , Boyer Breege , Briceño Henry , Stingl Ulrich
Published: May 2021

The Florida Keys, a delicate archipelago of sub-tropical islands extending from the south-eastern tip of Florida, host the vast majority of the only coral barrier reef in the continental United States. Abiotic as well as microbial components of the surrounding waters are pivotal for the health of reef habitats, and thus could play an important role in understanding the development and transmission of coral diseases in Florida. In this study, we analyzed microbial community structure and abiotic factors in waters around the Florida Reef Tract. Both bacterial and eukaryotic community structure were significantly linked with variations in temperature, dissolved oxygen, and total organic carbon values. High abundances of copiotrophic bacteria as well as several potentially harmful microbes, including coral pathogens, fish parasites and taxa that have been previously associated with Red Tide and shellfish poisoning were present in our datasets and may have a pivotal impact on reef health in this ecosystem.
Long-Term Effects of Dietary Supplementation with Olive Oil and Hydrogenated Vegetable Oil on the Rumen Microbiome of Dairy Cows
Authors: Cancino-Padilla Nathaly , Catalán Natalia , Siu-Ting Karen , Creevey Christopher J. , Huws Sharon A. , Romero Jaime , Vargas-Bello-Pérez Einar
Published: May 2021

Dietary lipids increase energy density in dairy cow diets and in some cases can increase beneficial fatty acids (FA) in milk and dairy products. However, the degree of FA saturation may affect the rumen microbiome. The objective of this study was to determine the long-term effects of feeding saturated (hydrogenated vegetable oil; HVO) or unsaturated (olive oil; OO) fatty acid (FA) sources on the rumen microbiome of dairy cows. For 63 days, 15 mid-lactating cows were fed with either a basal diet (no fat supplement), or the basal diet supplemented with 3% dry matter (DM), either HVO or OO. Rumen contents were collected on days 21, 42 and 63 for 16S rRNA gene sequencing using the Illumina MiSeq platform. The results reveal dominance of the phyla Firmicutes (71.5%) and Bacteroidetes (26.2%), and their respective prevalent genera Succiniclasticum (19.4%) and Prevotella (16.6%). Succiniclasticum increased with both treatments at all time points. Prevotella was reduced on day 42 in both diets. Bacterial diversity alpha or beta were not affected by diets. Predicted bacterial functions by CowPI showed changes in energy and protein metabolism. Overall, 3% DM of lipid supplementation over 63 days can be used in dairy cow diets without major impacts on global bacterial community structure.
Bile Salt Hydrolases: At the Crossroads of Microbiota and Human Health
Authors: Bourgin Mélanie , Kriaa Aicha , Mkaouar Héla , Mariaule Vincent , Jablaoui Amin , Maguin Emmanuelle , Rhimi Moez
Published: May 2021

The gut microbiota has been increasingly linked to metabolic health and disease over the last few decades. Several factors have been suggested to be involved in lipid metabolism and metabolic responses. One mediator that has gained great interest as a clinically important enzyme is bile salt hydrolase (BSH). BSH enzymes are widely distributed in human gastrointestinal microbial communities and are believed to play key roles in both microbial and host physiology. In this review, we discuss the current evidence related to the role of BSHs in health and provide useful insights that may pave the way for new therapeutic targets in human diseases.
Pan-Genome Analysis Reveals Host-Specific Functional Divergences in Burkholderia gladioli
Authors: Lee Hyun-Hee , Park Jungwook , Jung Hyejung , Seo Young-Su
Published: May 2021

Burkholderia gladioli has high versatility and adaptability to various ecological niches. Here, we constructed a pan-genome using 14 genome sequences of B. gladioli, which originate from different niches, including gladiolus, rice, humans, and nature. Functional roles of core and niche-associated genomes were investigated by pathway enrichment analyses. Consequently, we inferred the uniquely important role of niche-associated genomes in (1) selenium availability during competition with gladiolus host; (2) aromatic compound degradation in seed-borne and crude oil-accumulated environments, and (3) stress-induced DNA repair system/recombination in the cystic fibrosis-niche. We also identified the conservation of the rhizomide biosynthetic gene cluster in all the B. gladioli strains and the concentrated distribution of this cluster in human isolates. It was confirmed the absence of complete CRISPR/Cas system in both plant and human pathogenic B. gladioli and the presence of the system in B. gladioli living in nature, possibly reflecting the inverse relationship between CRISPR/Cas system and virulence.
Persistence of Coxsackievirus B4 in Pancreatic β Cells Disturbs Insulin Maturation, Pattern of Cellular Proteins, and DNA Methylation
Authors: Nekoua Magloire Pandoua , Bertin Antoine , Sane Famara , Gimeno Jean-Pascal , Fournier Isabelle , Salzet Michel , Engelmann Ilka , Alidjinou Enagnon Kazali , Hober Didier
Published: May 2021

Coxsackievirus-B4 (CV-B4) can persist in pancreatic cell lines and impair the phenoytpe and/or gene expressions in these cells; however, the models used to study this phenomenon did not produce insulin. Therefore, we investigated CV-B4 persistence and its consequences in insulin-producing pancreatic β cells. The insulin-secreting rat β cell line, INS-1, was infected with CV-B4. After lysis of a large part of the cell layer, the culture was still maintained and no additional cytopathic effect was observed. The amount of insulin in supernatants of cell cultures persistently infected with CV-B4 was not affected by the infection; in fact, a larger quantity of proinsulin was found. The mRNA expression of pro-hormone convertase 2, an enzyme involved in the maturation of proinsulin into insulin and studied using real-time reverse transcription-polymerase chain reaction, was inhibited in infected cultures. Further, the pattern of 47 cell proteins analyzed using Shotgun mass spectrometry was significantly modified. The DNA of persistently infected cell cultures was hypermethylated unlike that of controls. The persistent infection of INS-1 cells with CV-B4 had a deep impact on these cells, especially on insulin metabolism. Cellular changes caused by persistent CV-B4 infection of β cells can play a role in type 1 diabetes pathogenesis.
Survey of Pathogen-Lowering and Immuno-Modulatory Effects Upon Treatment of Campylobacter coli-Infected Secondary Abiotic IL-10−/− Mice with the Probiotic Formulation Aviguard®
Authors: Weschka Dennis , Mousavi Soraya , Biesemeier Nina , Bereswill Stefan , Heimesaat Markus M.
Published: May 2021

The prevalence of infections with the zoonotic enteritis pathogen Campylobacter coli is increasing. Probiotic formulations constitute promising antibiotic-independent approaches to reduce intestinal pathogen loads and modulate pathogen-induced immune responses in the infected human host, resulting in acute campylobacteriosis and post-infectious sequelae. Here, we address potential antipathogenic and immuno-modulatory effects of the commercial product Aviguard® during experimental campylobacteriosis. Secondary abiotic IL-10−/− mice were infected with a C. coli patient isolate on days 0 and 1, followed by oral Aviguard® treatment on days 2, 3 and 4. Until day 6 post-infection, Aviguard® treatment could lower the pathogen burdens within the proximal but not the distal intestinal tract. In contrast, the probiotic bacteria had sufficiently established in the intestines with lower fecal loads of obligate anaerobic species in C. coli-infected as compared to uninfected mice following Aviguard® treatment. Aviguard® application did not result in alleviated clinical signs, histopathological or apoptotic changes in the colon of infected IL-10−/− mice, whereas, however, Aviguard® treatment could dampen pathogen-induced innate and adaptive immune responses in the colon, accompanied by less distinct intestinal proinflammatory cytokine secretion. In conclusion, Aviguard® constitutes a promising probiotic compound to alleviate enteropathogen-induced proinflammatory immune responses during human campylobacteriosis.
Colletotrichum spp. from Soybean Cause Disease on Lupin and Can Induce Plant Growth-Promoting Effects
Authors: Wirtz Louisa , Massola Júnior Nelson Sidnei , Castro Renata Rebellato Linhares de , Ruge-Wehling Brigitte , Schaffrath Ulrich , Loehrer Marco
Published: May 2021

Protein crop plants such as soybean and lupin are attracting increasing attention because of their potential use as forage, green manure, or for the production of oil and protein for human consumption. Whereas soybean production only recently gained more importance in Germany and within the whole EU in frame of protein strategies, lupin production is already well-established in Germany. The cultivation of lupins is impeded by the hemibiotrophic ascomycete Colletotrichum lupini, the causal agent of anthracnose disease. Worldwide, soybean is also a host for a variety of Colletotrichum species, but so far, this seems to not be the case in Germany. Cross-virulence between lupin- and soybean-infecting isolates is a potential threat, especially considering the overlap of possible soybean and lupin growing areas in Germany. To address this question, we systematically investigated the interaction of different Colletotrichum species isolated from soybean in Brazil on German soybean and lupin plant cultivars. Conversely, we tested the interaction of a German field isolate of C. lupini with soybean. Under controlled conditions, Colletotrichum species from soybean and lupin were able to cross-infect the other host plant with varying degrees of virulence, thus underpinning the potential risk of increased anthracnose diseases in the future. Interestingly, we observed a pronounced plant growth-promoting effect for some host–pathogen combinations, which might open the route to the use of beneficial biological agents in lupin and soybean production.
MAIT Cells and Microbiota in Multiple Sclerosis and Other Autoimmune Diseases
Authors: Mechelli Rosella , Romano Silvia , Romano Carmela , Morena Emanuele , Buscarinu Maria Chiara , Bigi Rachele , Bellucci Gianmarco , Reniè Roberta , Pellicciari Giulia , Salvetti Marco , Ristori Giovanni
Published: May 2021

The functions of mucosal-associated invariant T (MAIT) cells in homeostatic conditions include the interaction with the microbiota and its products, the protection of body barriers, and the mounting of a tissue-repair response to injuries or infections. Dysfunction of MAIT cells and dysbiosis occur in common chronic diseases of inflammatory, metabolic, and tumor nature. This review is aimed at analyzing the changes of MAIT cells, as well as of the microbiota, in multiple sclerosis and other autoimmune disorders. Common features of dysbiosis in these conditions are the reduced richness of microbial species and the unbalance between pro-inflammatory and immune regulatory components of the gut microbiota. The literature concerning MAIT cells in these disorders is rather complex, and sometimes not consistent. In multiple sclerosis and other autoimmune conditions, several studies have been done, or are in progress, to find correlations between intestinal permeability, dysbiosis, MAIT cell responses, and clinical biomarkers in treated and treatment-naïve patients. The final aims are to explain what activates MAIT cells in diseases not primarily infective, which interactions with the microbiota are potentially pathogenic, and their dynamics related to disease course and disease-modifying treatments.
Novel Plant-Associated Acidobacteria Promotes Growth of Common Floating Aquatic Plants, Duckweeds
Authors: Yoneda Yasuko , Yamamoto Kyosuke , Makino Ayaka , Tanaka Yasuhiro , Meng Xian-Ying , Hashimoto Junko , Shin-ya Kazuo , Satoh Noriyuki , Fujie Manabu , Toyama Tadashi , Mori Kazuhiro , Ike Michihiko , Morikawa Masaaki , Kamagata Yoichi , Tamaki Hideyuki
Published: May 2021

Duckweeds are small, fast growing, and starch- and protein-rich aquatic plants expected to be a next generation energy crop and an excellent biomaterial for phytoremediation. Despite such an importance, very little is known about duckweed–microbe interactions that would be a key biological factor for efficient industrial utilization of duckweeds. Here we first report the duckweed growth promoting ability of bacterial strains belonging to the phylum Acidobacteria, the members of which are known to inhabit soils and terrestrial plants, but their ecological roles and plant–microbe interactions remain largely unclear. Two novel Acidobacteria strains, F-183 and TBR-22, were successfully isolated from wild duckweeds and phylogenetically affiliated with subdivision 3 and 6 of the phylum, respectively, based on 16S rRNA gene sequence analysis. In the co-culture experiments with aseptic host plants, the F-183 and TBR-22 strains visibly enhanced growth (frond number) of six duckweed species (subfamily Lemnoideae) up to 1.8–5.1 times and 1.6–3.9 times, respectively, compared with uninoculated controls. Intriguingly, both strains also increased the chlorophyll content of the duckweed (Lemna aequinoctialis) up to 2.4–2.5 times. Under SEM observation, the F-183 and TBR-22 strains were epiphytic and attached to the surface of duckweed. Taken together, our findings suggest that indigenous plant associated Acidobacteria contribute to a healthy growth of their host aquatic plants.
The Divergent Key Residues of Two Agrobacterium fabrum (tumefaciens) CheY Paralogs Play a Key Role in Distinguishing Their Functions
Authors: Gao Dawei , Zong Renjie , Huang Zhiwei , Ye Jingyang , Wang Hao , Xu Nan , Guo Minliang
Published: May 2021

The chemotactic response regulator CheY, when phosphorylated by the phosphoryl group from phosphorylated CheA, can bind to the motor switch complex to control the flagellar motor rotation. Agrobacterium fabrum (previous name: Agrobacterium tumefaciens), a phytopathogen, carries two paralogous cheY genes, cheY1 and cheY2. The functional difference of two paralogous CheYs remains unclear. Three cheY-deletion mutants were constructed to test the effects of two CheYs on the chemotaxis of A.fabrum. Phenotypes of three cheY-deletion mutants show that deletion of each cheY significantly affects the chemotactic response, but cheY2-deletion possesses more prominent effects on the chemotactic migration and swimming pattern of A. fabrum than does cheY1-deletion. CheA-dependent cellular localization of two CheY paralogs and in vitro pull-down of two CheY paralogs by FliM demonstrate that the distinct roles of two CheY paralogs arise mainly from the differentiation of their binding affinities for the motor switch component FliM, agreeing with the divergence of the key residues on the motor-binding surface involved in the interaction with FliM. The single respective replacements of key residues R93 and A109 on the motor-binding surface of CheY2 by alanine (A) and valine (V), the corresponding residues of CheY1, significantly enhanced the function of CheY2 in regulating the chemotactic response of A. fabrum CheY-deficient mutant Δy to nutrient substances and host attractants. These results conclude that the divergence of the key residues in the functional subdomain is the decisive factor of functional differentiation of these two CheY homologs and protein function may be improved by the substitution of the divergent key residues in the functional domain for the corresponding residues of its paralogs. This finding will help us to better understand how paralogous proteins sub-functionalize. In addition, the acquirement of two CheY2 variants, whose chemotactic response functions are significantly improved, will be very useful for us to further explore the mechanism of CheY to bind and regulate the flagellar motor and the role of chemotaxis in the pathogenicity of A. fabrum.
Spatial Component Analysis to Improve Mineral Estimation Using Sentinel-2 Band Ratio: Application to a Greek Bauxite Residue
Authors: Bruno Roberto , Kasmaeeyazdi Sara , Tinti Francesco , Mandanici Emanuele , Balomenos Efthymios
Published: May 2021

Remote sensing can be fruitfully used in the characterization of metals within stockpiles and tailings, produced from mining activities. Satellite information, in the form of band ratio, can act as an auxiliary variable, with a certain correlation with the ground primary data. In the presence of this auxiliary variable, modeled with nested structures, the spatial components without correlation can be filtered out, so that the useful correlation with ground data grows. This paper investigates the possibility to substitute in a co-kriging system, the whole band ratio information, with only the correlated components. The method has been applied over a bauxite residues case study and presents three estimation alternatives: ordinary kriging, co-kriging, component co-kriging. Results have shown how using the most correlated component reduces the estimation variance and improves the estimation results. In general terms, when a good correlation with ground samples exists, co-kriging of the satellite band-ratio Component improves the reconstruction of mineral grade distribution, thus affecting the selectivity. On the other hand, the use of the components approach exalts the distance variability.
Methodological Approach (In Situ and Laboratory) for the Characterisation of Late Prehistoric Rock Paintings—Penedo Gordo (NW Spain)
Authors: Pozo-Antonio Jose Santiago , Comendador Rey Beatriz , Alves Bacelar Lara , Barreiro Pablo
Published: May 2021

This paper draws on the study of the prehistoric art site of Penedo Gordo (NW Spain) resulting from a collaborative interdisciplinary research. One of its primary goals was to design and put into practice a multi-analytical protocol for characterising prehistoric rock paintings, combining in situ and laboratory analytical techniques. Thus, following the archaeological assessment of the site, the panels exhibiting red paintings were analysed by colour spectrophotometry and portable Raman spectroscopy. Analytical techniques were applied to a collection of samples exhumed from the excavation that simultaneously took place on site. These included three red accretions on different substrates (compact soil, white quartzite and grey quartzite) and stone fragments representative of the outcrop’s petrographic variability, aiming to determine their mineralogical composition, texture and study the stone-paint boundaries. Moreover, colouring materials exhumed from the excavation and collected in the immediate surroundings of the rock outcrop were analysed in order to scrutinise the provenience rock art’s raw materials. Laboratory analysis consisted of stereomicroscopy, X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. One of the major outcomes was the discovery of a drop of red pigment preserved in an archaeological layer associated with Late Neolithic/Copper Age material remains.
A Novel Calcium Oxalate/Sepiolite Composite for Highly Selective Adsorption of Pb(II) from Aqueous Solutions
Authors: Xie Hui , Zhang Shilin , Liu Jingyan , Hu Jinqing , Tang Aidong
Published: May 2021

Synthesizing functional nanomaterials from naturally abundant clay has always been of vital importance for resource utilization, however, the lack of new methods to effectively utilize low-grade clay presents a significant challenge. Herein, a calcium oxalate/sepiolite nanocomposite (SMN-x) was prepared by using the water bath heating method to convert the associated calcium carbonate in low-grade sepiolite into calcium oxalate. The developed composite was subsequently used to remove Pb(II) from the aqueous solutions. The SMN-3 adsorbent prepared by heating in a water bath at 90 °C for 3 h (with a high specific surface area of 234.14 m2·g−1) revealed the maximum Pb(II) adsorption capacity of 504.07 mg·g−1 at pH 5, which was about five times higher than that of sepiolite (105.57 mg·g−1). Further, the SMN-3 adsorbent possessed a much higher selectivity for Pb(II) as compared to the other metal ions. Moreover, the residue was noted to be stable and safe. The adsorption kinetics and isotherms conformed to the quasi-second-order kinetic and Langmuir models. During the adsorption process, ion exchange was noted to the main mechanism, however, it was also accompanied by electrostatic attraction. This study provides a novel strategy for the sustainable development of simple and efficient adsorbents by utilizing low-grade clay minerals.
Rutile Mineral Chemistry and Zr-in-Rutile Thermometry in Provenance Study of Albian (Uppermost Lower Cretaceous) Terrigenous Quartz Sands and Sandstones in Southern Extra-Carpathian Poland
Authors: Kotowski Jakub , Nejbert Krzysztof , Olszewska-Nejbert Danuta
Published: May 2021

The geochemistry of detrital rutile grains, which are extremely resistant to weathering, was used in a provenance study of the transgressive Albian quartz sands in the southern part of extra-Carpathian Poland. Rutile grains were sampled from eight outcrops and four boreholes located on the Miechów, Szydłowiec, and Puławy Segments. The crystallization temperatures of the rutile grains, calculated using a Zr-in-rutile geothermometer, allowed for the division of the study area into three parts: western, central, and eastern. The western group of samples, located in the Miechów Segment, is characterized by a polymodal distribution of rutile crystallization temperatures (700–800 °C; 550–600 °C, and c. 900 °C) with a significant predominance of high-temperature forms, and with a clear prevalence of metapelitic over metamafic rutile. The eastern group of samples, corresponding to the Lublin Area, is monomodal and their crystallization temperatures peak at 550–600 °C. The contents of metapelitic to metamafic rutile in the study area are comparable. The central group of rutile samples with bimodal distribution (550–600 °C and 850–950 °C) most likely represents a mixing zone, with a visible influence from the western and, to a lesser extent, the eastern group. The most probable source area for the western and the central groups seems to be granulite and high-temperature eclogite facies rocks from the Bohemian Massif. The most probable source area for the eastern group of rutiles seems to be amphibolites and low temperature eclogite facies rocks, probably derived from the southern part of the Baltic Shield.
Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds
Authors: Levi Elena , Aurbach Doron , Gatti Carlo
Published: May 2021

Most of TM6-cluster compounds (TM = transition metal) are soluble in polar solvents, in which the cluster units commonly remain intact, preserving the same atomic arrangement as in solids. Consequently, the redox potential is often used to characterize structural and electronic features of respective solids. Although a high lability and variety of ligands allow for tuning of redox potential and of the related spectroscopic properties in wide ranges, the mechanism of this tuning is still unclear. Crystal chemistry approach was applied for the first time to clarify this mechanism. It was shown that there are two factors affecting redox potential of a given metal couple: Lever’s electrochemical parameters of the ligands and the effective ionic charge of TM, which in cluster compounds differs effectively from the formal value due to the bond strains around TM atoms. Calculations of the effective ionic charge of TMs were performed in the framework of bond valence model, which relates the valence of a bond to its length by simple Pauling relationship. It was also shown that due to the bond strains the charge depends mainly on the atomic size of the inner ligands.
Attempts for Developing Novel Sugar-Based and Sugar-Free Sea Buckthorn Marmalades
Authors: Nistor Oana-Viorela , Bolea Carmen Alina , Andronoiu Doina-Georgeta , Cotârleț Mihaela , Stănciuc Nicoleta
Published: May 2021

Sea buckthorn (Hippophaė rhamnoides L.) is recognized as a valuable source of vitamin C and antioxidants, frequently used as nutraceuticals and cosmeceuticals. In the present study, attempts are made to produce and characterize a novel type of marmalade using sea buckthorn berries processed at 102 °C into marmalade in two combinations, with whole cane or stevia sugar. Changes in the phytochemical profile, antioxidant activity, color, shelf-life, texture, microbiological, and sensorial characteristics were determined. The total carotenoids content in the marmalades were significantly different, with values of 0.91 ± 0.03 mg/g dry weight (DW) in the sample with whole sugar cane (Cz) and 2.69 ± 0.14 mg/g DW in the sample with Stevia sugar (Cs). Significant values of polyphenols were found, of 59.41 ± 1.13 mg GAE/g DW in Cz and 72.44 ± 2.31 mg GAE/g DW in Cs, leading to an antioxidant activity of 45.12 ± 0.001 μMol Trolox/g DW and 118.07 ± 0.01 μMol Trolox/g DW, respectively. Accelerated storage study showed a decrease in all the phytochemicals, however no significant changes were found in antioxidant activity. Values of <100 CFU/g for yeasts and molds and <5 CFU/g for Enterobacteriaceae after 21 days of storage at the room temperature of the marmalades were determined. The sensorial and color results were more than acceptable. Overall, the results highlighted the potential of using sea buckthorn as a potential rich source of bioactive compounds to be used in the sugar-based products manufacturing.
Electrochemical Assessment of Indigo Carmine Dye in Lithium Metal Polymer Technology
Authors: Lécuyer Margaud , Deschamps Marc , Guyomard Dominique , Gaubicher Joël , Poizot Philippe
Published: May 2021

Lithium metal batteries are inspiring renewed interest in the battery community because the most advanced designs of Li-ion batteries could be on the verge of reaching their theoretical specific energy density values. Among the investigated alternative technologies for electrochemical storage, the all-solid-state Li battery concept based on the implementation of dry solid polymer electrolytes appears as a mature technology not only to power full electric vehicles but also to provide solutions for stationary storage applications. With an effective marketing started in 2011, BlueSolutions keeps developing further the so-called lithium metal polymer batteries based on this technology. The present study reports the electrochemical performance of such Li metal batteries involving indigo carmine, a cheap and renewable electroactive non-soluble organic salt, at the positive electrode. Our results demonstrate that this active material was able to reversibly insert two Li at an average potential of ≈2.4 V vs. Li+/Li with however, a relatively poor stability upon cycling. Post-mortem analyses revealed the poisoning of the Li electrode by Na upon ion exchange reaction between the Na countercations of indigo carmine and the conducting salt. The use of thinner positive electrodes led to much better capacity retention while enabling the identification of two successive one-electron plateaus.
Unexpected Radical Telomerisation of Vinylidene Fluoride with 2-Mercaptoethanol
Authors: Duc Michel , Boutevin Bernard , Ameduri Bruno
Published: May 2021

The radical telomerisation of vinylidene fluoride (VDF) with 2-mercaptoethanol as chain transfer agent (CTA) was studied to synthesise fluorinated telomers which bear a hydroxy end-group, such as H(VDF)nS(CH2)2OH, under thermal (di-tert-butyl peroxide as the initiator) or photochemical initiations. A careful structural study of a typical H-VDF-S(CH2)2OH telomer was performed by 1H and 19F NMR spectroscopy. These analytical methods allowed us to explore the selective addition of the thiyl radical onto the hydrogenated side of VDF, and the telomer containing one VDF unit was obtained selectively. Surprisingly, for higher [VDF]o initial concentrations, a monoadduct telomer was produced as well as PVDF homopolymer. This feature was related to the fast consumption of the CTA. The kinetics of radical telomerisation led to a quite high transfer constant of the CTA (40 at 140 °C) that evidences the formation of a monoadduct as the only telomer formed.
A Portrait of the OPE as a Biological Agent
Authors: Gangemi Chiara Maria Antonietta , Barattucci Anna , Bonaccorsi Paola Maria
Published: May 2021

Oligophenylene ethynylenes, known as OPEs, are a sequence of aromatic rings linked by triple bonds, the properties of which can be modulated by varying the length of the rigid main chain or/and the nature and position of the substituents on the aromatic units. They are luminescent molecules with high quantum yields and can be designed to enter a cell and act as antimicrobial and antiviral compounds, as biocompatible fluorescent probes directed towards target organelles in living cells, as labelling agents, as selective sensors for the detection of fibrillar and prefibrillar amyloid in the proteic field and in a fluorescence turn-on system for the detection of saccharides, as photosensitizers in photodynamic therapy (due to their capacity to highly induce toxicity after light activation), and as drug delivery systems. The antibacterial properties of OPEs have been the most studied against very popular and resistant pathogens, and in this paper the achievements of these studies are reviewed, together with almost all the other roles held by such oligomers. In the recent decade, their antifungal and antiviral effects have attracted the attention of researchers who believe OPEs to be possible biocides of the future. The review describes, for instance, the preliminary results obtained with OPEs against severe acute respiratory syndrome coronavirus 2, the virus responsible for the COVID-19 pandemic.
Recent Progress in Transdermal Nanocarriers and Their Surface Modifications
Authors: Yu Zhixi , Meng Xinxian , Zhang Shunuo , Chen Yunsheng , Zhang Zheng , Zhang Yixin
Published: May 2021

Transdermal drug delivery system (TDDS) is an attractive method for drug delivery with convenient application, less first-pass effect, and fewer systemic side effects. Among all generations of TDDS, transdermal nanocarriers show the greatest clinical potential because of their non-invasive properties and high drug delivery efficiency. However, it is still difficult to design optimal transdermal nanocarriers to overcome the skin barrier, control drug release, and achieve targeting. Hence, surface modification becomes a promising strategy to optimize and functionalize the transdermal nanocarriers with enhanced penetration efficiency, controlled drug release profile, and targeting drug delivery. Therefore, this review summarizes the developed transdermal nanocarriers with their transdermal mechanism, and focuses on the surface modification strategies via their different functions.
Synthesis and Guest-Binding Properties of pH/Reduction Dual-Responsive Cyclophane Dimer
Authors: Hayashida Osamu , Tanaka Yudai , Miyazaki Takaaki
Published: May 2021

A water-soluble cyclophane dimer having two disulfide groups as a reduction-responsive cleavable bond as well as several acidic and basic functional groups as a pH-responsive ionizable group 1 was successfully synthesized. It was found that 1 showed pH-dependent guest-binding behavior. That is, 1 strongly bound an anionic guest, 6-p-toluidinonaphthalene-2-sulfonate (TNS) with binding constant (K/M−1) for 1:1 host-guest complexes of 9.6 × 104 M−1 at pH 3.8, which was larger than those at pH 7.4 and 10.7 (6.0 × 104 and 2.4 × 104 M−1, respectively), indicating a favorable electrostatic interaction between anionic guest and net cationic 1. What is more, release of the entrapped guest molecules by 1 was easily controlled by pH stimulus. Large favorable enthalpies (ΔH) for formation of host-guest complexes were obtained under the pH conditions employed, suggesting that electrostatic interaction between anionic TNS and 1 was the most important driving force for host-guest complexation. Such contributions of ΔH for formation of host-guest complexes decreased along with increased pH values from acidic to basic solutions. Upon addition of dithiothreitol (DTT) as a reducing reagent to an aqueous PBS buffer (pH 7.4) containing 1 and TNS, the fluorescence intensity originating from the bound guest molecules decreased gradually. A treatment of 1 with DTT gave 2, having less guest-binding affinity by the cleavage of disulfide bonds of 1. Consequently, almost all entrapped guest molecules by 1 were released from the host. Moreover, such reduction-responsive cleavage of 1 and release of bound guest molecules was performed more rapidly in aqueous buffer at pH 10.7.
Influence of the Phenological Stage and Harvest Date on the Bioactive Compounds Content of Green Pepper Fruit
Authors: Dobón-Suárez Alicia , Giménez María J. , Castillo Salvador , García-Pastor María E. , Zapata Pedro J.
Published: May 2021

Green pepper fruit is often consumed before it is completely ripe. However, the influence of the phenological stage in which the green pepper is consumed as a potential influencing factor in its bioactive compounds content and antioxidant capacity remains unknown. In addition, no literature is available concerning the bioactive compounds changes in ‘Lamuyo’ green peppers along its developmental and growth cycle. For this, two different approaches have been carried out, one using twelve different phenological stages (S1 to S12), and in the other, seven different harvest dates (from 27 February to 20 April). Moreover, bioactive compounds changes during 21 days of postharvest storage at 8 °C were investigated. In this study, bioactive compounds (ascorbic acid, dehydroascorbic acid, and total phenolic content) and the total hydrophilic and lipophilic (TAA-H and TAA-L) antioxidant activity were analysed. In addition, total soluble solids, total acidity, individual sugars, and organic acids were determined. Vitamin C levels increased along the phenological stages and harvest dates due to significant increases in ascorbic and dehydroascorbic acid levels. Our results show that the total phenol content decreases as vegetables develop and subsequently increases both as ripening begins and by the last harvest date. Furthermore, TAA-H was also greater by the phenological stage S12 and the 20 April harvest date. In conclusion, the phenological stage and harvest date are key factors that significantly influence the bioactive compounds of green peppers, and those that appear by S12 and 20 April could be more beneficial to health.
Application of Bar Adsorptive Microextraction for the Determination of Levels of Tricyclic Antidepressants in Urine Samples
Authors: Oliveira Mariana N. , Gonçalves Oriana C. , Ahmad Samir M. , Schneider Jaderson K. , Krause Laiza C. , Neng Nuno R. , Caramão Elina B. , Nogueira José M. F.
Published: May 2021

This work entailed the development, optimization, validation, and application of a novel analytical approach, using the bar adsorptive microextraction technique (BAμE), for the determination of the six most common tricyclic antidepressants (TCAs; amitriptyline, mianserin, trimipramine, imipramine, mirtazapine and dosulepin) in urine matrices. To achieve this goal, we employed, for the first time, new generation microextraction devices coated with convenient sorbent phases, polymers and novel activated carbons prepared from biomaterial waste, in combination with large-volume-injection gas chromatography-mass spectrometry operating in selected-ion monitoring mode (LVI-GC-MS(SIM)). Preliminary assays on sorbent coatings, showed that the polymeric phases present a much more effective performance, as the tested biosorbents exhibited low efficiency for application in microextraction techniques. By using BAμE coated with C18 polymer, under optimized experimental conditions, the detection limits achieved for the six TCAs ranged from 0.2 to 1.6 μg L−1 and, weighted linear regressions resulted in remarkable linearity (r2 > 0.9960) between 10.0 and 1000.0 μg L−1. The developed analytical methodology (BAμE(C18)/LVI-GC-MS(SIM)) provided suitable matrix effects (90.2–112.9%, RSD ≤ 13.9%), high recovery yields (92.3–111.5%, RSD ≤ 12.3%) and a remarkable overall process efficiency (ranging from 84.9% to 124.3%, RSD ≤ 13.9%). The developed and validated methodology was successfully applied for screening the six TCAs in real urine matrices. The proposed analytical methodology proved to be an eco-user-friendly approach to monitor trace levels of TCAs in complex urine matrices and an outstanding analytical alternative in comparison with other microextraction-based techniques.
Metoprolol and Its Degradation and Transformation Products Using AOPs—Assessment of Aquatic Ecotoxicity Using QSAR
Authors: Voigt Melanie , Bartels Indra , Schmiemann Dorothee , Votel Lars , Hoffmann-Jacobsen Kerstin , Jaeger Martin
Published: May 2021

Pharmaceuticals are found in waterbodies worldwide. Conventional sewage treatment plants are often not able to eliminate these micropollutants. Hence, Advanced Oxidation Processes (AOPs) have been heavily investigated. Here, metoprolol is exposed to UV irradiation, hydrogen peroxide, and ozonation. Degradation was analyzed using chemical kinetics both for initial and secondary products. Photo-induced irradiation enhanced by hydrogen peroxide addition accelerated degradation more than ozonation, leading to complete elimination. Degradation and transformation products were identified by high-performance liquid-chromatography coupled to high-resolution higher-order mass spectrometry. The proposed structures allowed to apply Quantitative Structure-Activity Relationship (QSAR) analysis to predict ecotoxicity. Degradation products were generally associated with a lower ecotoxicological hazard to the aquatic environment according to OECD QSAR toolbox and VEGA. Comparison of potential structural isomers suggested forecasts may become more reliable with larger databases in the future.