bluuebunny/crossref_metadata_2025 huggingface dataset:
Generalised S-System-Type Equation: Sensitivity of the Deterministic and Stochastic Models for Bone Mechanotransduction
Authors: Simonović Julijana , Woolley Thomas E.
Published: September 2021

The formalism of a bone cell population model is generalised to be of the form of an S-System. This is a system of nonlinear coupled ordinary differential equations (ODEs), each with the same structure: the change in a variable is equal to a difference in the product of a power-law functions with a specific variable. The variables are the densities of a variety of biological populations involved in bone remodelling. They will be specified concretely in the cases of a specific periodically forced system to describe the osteocyte mechanotransduction activities. Previously, such models have only been deterministically simulated causing the populations to form a continuum. Thus, very little is known about how sensitive the model of mechanotransduction is to perturbations in parameters and noise. Here, we revisit this assumption using a Stochastic Simulation Algorithm (SSA), which allows us to directly simulate the discrete nature of the problem and encapsulate the noisy features of individual cell division and death. Critically, these stochastic features are able to cause unforeseen dynamics in the system, as well as completely change the viable parameter region, which produces biologically realistic results.
Echinochrome A Protects against Ultraviolet B-induced Photoaging by Lowering Collagen Degradation and Inflammatory Cell Infiltration in Hairless Mice
Authors: Seol Jung Eun , Ahn Sang Woo , Seol Bomin , Yun Hyeong Rok , Park Nammi , Kim Hyoung Kyu , Vasileva Elena A. , Mishchenko Natalia P. , Fedoreyev Sergey A. , Stonik Valentin A. , Han Jin
Published: September 2021

Echinochrome A (Ech A, 7-ethyl-2,3,5,6,8-pentahydroxy-1,4-naphthoquinone) has been known to exhibit anti-oxidative and anti-inflammatory effects. However, no study has been carried out on the efficacy of Ech A against skin photoaging; this process is largely mediated by oxidative stress. Six-week-old male SKH-1 hairless mice (n = 36) were divided into five groups. Except for a group that were not treated (n = 4), all mice underwent ultraviolet-B (UVB) exposure for 8 weeks while applying phosphate-buffered saline or Ech A through intraperitoneal injection. UVB impaired skin barrier function, showing increased transepidermal water loss and decreased stratum corneum hydration. UVB induced dermal collagen degeneration and mast cell infiltration. Ech A injection was found to significantly lower transepidermal water loss while attenuating tissue inflammatory changes and collagen degeneration compared to the control. Furthermore, Ech A was found to decrease the relative expression of matrix metalloproteinase, tryptase, and chymase. Taken together, these results suggest that Ech A protects against UVB-induced photoaging in both functional and histologic aspects, causing a lowering of collagen degradation and inflammatory cell infiltration.
Neonatal Intrahepatic Cholestasis Caused by Citrin Deficiency with SLC25A13 Mutation Presenting Hepatic Steatosis and Prolonged Jaundice. A Rare Case Report
Authors: Hu Shu-Wei , Lu Wen-Li , Chiang I-Ping , Wu Shu-Fen , Wang Chung-Hsing , Chen An-Chyi
Published: September 2021

Background: Neonatal intrahepatic cholestasis caused by citrin deficiency (NICCD) is a rare autosomal recessive disease. The incidence of citrin deficiency is estimated between 1/10,000 and 1/20,000 in Taiwan. Case report: This report describes a case of a 42 day old female infant who suffered from prolonged jaundice, poor weight gain, and anemia. The initial total/direct bilirubin levels were 8.1/3.11 mg/dL. Liver biopsy was performed at 47 days old. The pathology revealed lobules marked with macrovesicular and microvesicular fatty metamorphosis. The serum amino acid profile showed elevated levels of threonine, methionine, citrulline, and arginine. Newborn screening disclosed normal results, but the genetic study revealed SLC25A13 mutation 851–854 del and 615 + 5G > A. The genetic study of her parents showed that the father carried the SLC25A13 mutation 851–854 del and the mother carried the SLC25A13 mutation 615 + 5G > A. Treatment with ursodeoxycholic acid decreased the bilirubin levels to a normal range at the age of 5 months. Conclusion: This report illustrates that hepatic steatosis is a feature of NICCD. For every young infant patient who develops cholestasis, the pediatrician must consider NICCD as a differential diagnosis even if newborn screening shows normal findings.
Inherited/Genetically-Associated Pheochromocytoma/ Paraganglioma Syndromes and COVID-19
Authors: Ilias Ioannis , Kaltsas Gregory , Barkas Konstantinos , Chrousos George P.
Published: September 2021

In some subjects with inherited pheochromocytoma/paraganglioma (PPG) syndromes, hypoxia-inducible factor 1 alpha (HIF1α) stabilization/activation could lead to an increase in angiotensin converting enzymes (ACE). This would result in the stimulation of angiotensin (AT) II production and, hence, reduce the availability of ACE 2. The latter would provide decreased numbers of binding sites for the spike protein of SARS-CoV-2 and, therefore, result in less points of viral entry into cells. Thus, subjects with HIF1α-associated PPG syndromes may benefit from an inherent protective effect against COVID-19. Such an implication of HIF1α vis-à-vis COVID-19 could open ways of therapeutic interventions.
Phase Lag Entropy as a Surrogate Measurement of Hypnotic Depth during Sevoflurane Anesthesia
Authors: Kim Kyung-Mi , Lee Ki-Hwa , Park Jae-Hong
Published: September 2021

Background and Objectives: Phase lag entropy, an electroencephalographic monitor, evaluates the variety in temporal patterns of phase relationship between frontal and prefrontal brain region. Phase lag entropy can reflect the depth of anesthesia induced by propofol, but the association between sevoflurane and phase lag entropy has not been elucidated. This study examined the effect of sevoflurane on phase lag entropy during induction of general anesthesia. We also explored the pharmacodynamic model between end-tidal anesthetic concentration and electroencephalographic monitor. Materials and Methods: A total of 20 patients were enrolled. General anesthesia was produced by escalating the sevoflurane (1 vol% up to 8 vol%). The relationship between phase lag entropy and end-tidal anesthetic concentration was analyzed. A non-linear mixed-effects model was used to get the relationship of pharmacodynamics between the end-tidal sevoflurane concentration and phase lag entropy. Mean blood pressure, heart rate, and the modified observer’s assessment of alertness/sedation scale were also recorded during sevoflurane anesthesia. Results: As level of sedation increased, phase lag entropy decreased. A significant correlation was showed between phase lag entropy and end-tidal sevoflurane concentration (r = −0.759, p < 0.001). The correlation coefficient between the modified observer’s assessment of alertness/sedation scale and phase lag entropy was 0.731 (p < 0.001). The pharmacodynamic factors assessed by the sigmoid Emax model were E0 = 84.9, Emax = 42, Ce50 = 1.81, γ = 4.78, and ke0 = 0.692. The prediction probability of phase-lag entropy for measuring the modified observer’s assessment of alertness/sedation scale and end-tidal sevoflurane concentration were 0.764 and 0.789, respectively. With the increasing concentration of sevoflurane, mean blood pressure decreased, but heart rate did not change. Conclusions: The continuing escalation in end-tidal sevoflurane concentration caused a decline in phase lag entropy. Phase lag entropy can serve as an indicator of hypnotic depth in patients receiving sevoflurane anesthesia.
Preliminary Study on Fish Scale Collagen Lamellar Matrix as Artificial Cornea
Authors: Cheng Guoping , Chen Liang , Feng Huanhuan , Jiang Bo , Ding Yi
Published: September 2021

To construct a novel artificial cornea biomaterial, a method to prepare collagen lamellar matrix was developed in this study using grass carp scales as raw materials. The relationship between the structure of fish scale collagen lamellar matrix and the optical and mechanical properties was analyzed, and co-culture of it and rat bone marrow mesenchymal stem cells (BMSCs) was performed to preliminarily analyze the cellular compatibility of fish scale collagen lamellar matrix. The results show that the grass carp scales could be divided into base region, lateral region and parietal region according to the surface morphology. The inorganic calcium in the surface layer could be effectively removed by decalcification, and the decalcification rate could reach 99%. After etching treatment, homogeneous collagen lamellar matrix could be obtained. With the decalcification and etching treatment, the water content of the sample increased gradually, but the cross-linking treatment had no obvious effect on the water content of fish scale collagen lamellar matrix. Fish scale collagen lamellar matrix has good transparency, refractive index, mechanical properties and cellular compatibility, which may represent a prospect for the construction of cornea tissue engineering products.
The Implications of Membranes Used as Separators in Microbial Fuel Cells
Authors: Ramirez-Nava Jonathan , Martínez-Castrejón Mariana , García-Mesino Rocío Lley , López-Díaz Jazmin Alaide , Talavera-Mendoza Oscar , Sarmiento-Villagrana Alicia , Rojano Fernando , Hernández-Flores Giovanni
Published: September 2021

Microbial fuel cells (MFCs) are electrochemical devices focused on bioenergy generation and organic matter removal carried out by microorganisms under anoxic environments. In these types of systems, the anodic oxidation reaction is catalyzed by anaerobic microorganisms, while the cathodic reduction reaction can be carried out biotically or abiotically. Membranes as separators in MFCs are the primary requirements for optimal electrochemical and microbiological performance. MFC configuration and operation are similar to those of proton-exchange membrane fuel cells (PEMFCs)—both having at least one anode and one cathode split by a membrane or separator. The Nafion® 117 (NF-117) membrane, made from perfluorosulfonic acid, is a membrane used as a separator in PEMFCs. By analogy of the operation between electrochemical systems and MFCs, NF-117 membranes have been widely used as separators in MFCs. The main disadvantage of this type of membrane is its high cost; membranes in MFCs can represent up to 60% of the MFC’s total cost. This is one of the challenges in scaling up MFCs: finding alternative membranes or separators with low cost and good electrochemical characteristics. The aim of this work is to critically review state-of-the-art membranes and separators used in MFCs. The scope of this review includes: (i) membrane functions in MFCs, (ii) most-used membranes, (iii) membrane cost and efficiency, and (iv) membrane-less MFCs. Currently, there are at least 20 different membranes or separators proposed and evaluated for MFCs, from basic salt bridges to advanced synthetic polymer-based membranes, including ceramic and unconventional separator materials. Studies focusing on either low cost or the use of natural polymers for proton-exchange membranes (PEM) are still scarce. Alternatively, in some works, MFCs have been operated without membranes; however, significant decrements in Coulombic efficiency were found. As the type of membrane affects the performance and total cost of MFCs, it is recommended that research efforts are increased in order to develop new, more economic membranes that exhibit favorable properties and allow for satisfactory cell performance at the same time. The current state of the art of membranes for MFCs addressed in this review will undoubtedly serve as a key insight for future research related to this topic.
Removal of Ibuprofen at Low Concentration Using a Newly Formulated Emulsion Liquid Membrane
Authors: Ahmad Abdul Latif , Mohd Harun Mohd Hazarel Zairy , Akmal Jasni Mohd Khairul , Zaulkiflee Nur Dina
Published: September 2021

Ibuprofen (IBP) is a pharmaceutical product that is widely prescribed as an over-the-counter painkiller. It has been classified as a contaminant of emerging concern (CEC) that has received global attention in the search for a better wastewater separation technology. The emulsion liquid membrane (ELM) is one of the potential solutions for IBP removal from wastewater owing to its advantages, such as the ability to remove a highly soluble solute, energy efficient and tuneable formulation. To develop this ELM, a series of parameters such as stirring speed, emulsification time, organic to internal phase volume ratio (O/I), internal phase concentration, carrier concentration and surfactant concentration were studied. The extraction was carried out for 15 min stirring time and the concentration of IBP in the feed phase was determined using a UV-Vis spectrophotometer. The optimum formulation for the ELM was found at 300 rpm stirring speed, 20 min emulsification time, 3:1 of O/I, 0.1 M ammonia, NH3 (stripping agent), 6 wt% trioctylamine, TOA (carrier) and 2 wt% sorbitan monooleate, Span 80 (non-ionic surfactant). IBP removal of 89% was achieved at the optimum parameters of ELM. The current research demonstrated that a newly formulated ELM has great potential in removing a low concentration IBP from wastewater.
Impact of the Recovery on Concentrating Acetic Acid with Low-Pressure Reverse-Osmosis Membranes
Authors: Pratofiorito Giorgio , Horn Harald , Saravia Florencia
Published: September 2021

This work deals with the optimization of the concentration of volatile fatty acids (VFAs) using low-pressure reverse osmosis (LPRO) membranes. Membrane filtration of a synthetic solution simulating the product of biomass hydrolysis was performed. Experiments were run on two flat-sheet XLE membranes under 22 and 25 bar in continuous operation mode. Separation efficiency was evaluated for different recoveries. A correlation between the osmotic pressure of the concentrate and the parameter Rc, representative of the separation efficiency, was found. Under the conditions of the present study and taking into consideration the rejection properties of the applied membrane, a recovery of 33% and 44% is recommendable to maximize the ratio between the concentration of acetate in the concentrate and permeate and thus increase the total reclaim of acetic acid.
In Utero Exposure to Persistent Organic Pollutants and Childhood Lipid Levels
Authors: Boutot Maegan E. , Whitcomb Brian W. , Abdelouahab Nadia , Baccarelli Andrea A. , Boivin Amélie , Caku Artuela , Gillet Virginie , Martinez Guillaume , Pasquier Jean-Charles , Zhu Jiping , Takser Larissa , St-Cyr Lindsay , Suvorov Alexander
Published: September 2021

Animal studies have shown that developmental exposures to polybrominated diphenyl ethers (PBDE) permanently affect blood/liver balance of lipids. No human study has evaluated associations between in utero exposures to persistent organic pollutants (POPs) and later life lipid metabolism. In this pilot, maternal plasma levels of PBDEs (BDE-47, BDE-99, BDE-100, and BDE-153) and polychlorinated biphenyls (PCB-138, PCB-153, and PCB-180) were determined at delivery in participants of GESTation and Environment (GESTE) cohort. Total cholesterol (TCh), triglycerides (TG), low- and high-density lipoproteins (LDL-C and HDL-C), total lipids (TL), and PBDEs were determined in serum of 147 children at ages 6–7. General linear regression was used to estimate the relationship between maternal POPs and child lipid levels with adjustment for potential confounders, and adjustment for childhood POPs. In utero BDE-99 was associated with lower childhood levels of TG (p = 0.003), and non-significantly with HDL-C (p = 0.06) and TL (p = 0.07). Maternal PCB-138 was associated with lower childhood levels of TG (p = 0.04), LDL-C (p = 0.04), and TL (p = 0.02). Our data indicate that in utero exposures to POPs may be associated with long lasting decrease in circulating lipids in children, suggesting increased lipid accumulation in the liver, a mechanism involved in NAFLD development, consistent with previously reported animal data.
CSF Metabolomics of Tuberculous Meningitis: A Review
Authors: Mason Shayne , Solomons Regan
Published: September 2021

From the World Health Organization’s global TB report for 2020, it is estimated that in 2019 at least 80,000 children (a particularly vulnerable population) developed tuberculous meningitis (TBM)—an invariably fatal disease if untreated—although this is likely an underestimate. As our latest technologies have evolved—with the unprecedented development of the various “omics” disciplines—a mountain of new data on infectious diseases have been created. However, our knowledge and understanding of infectious diseases are still trying to keep pace. Metabolites offer much biological information, but the insights they permit can be difficult to derive. This review summarizes current metabolomics studies on cerebrospinal fluid (CSF) from TBM cases and collates the metabolic data reported. Collectively, CSF metabolomics studies have identified five classes of metabolites that characterize TBM: amino acids, organic acids, nucleotides, carbohydrates, and “other”. Taken holistically, the information given in this review serves to promote the mechanistic action of hypothesis generation that will drive and direct future studies on TBM.
Naturally Occurring Glycosidases in Milk from Native Cattle Breeds: Activity and Consequences on Free and Protein Bound-Glycans
Authors: Sunds Anne Vuholm , Roland Ida Schwartz , Sundekilde Ulrik Kræmer , Thesbjerg Martin Nørmark , Robinson Randall , Bunyatratchata Apichaya , Glantz Maria , Paulsson Marie , Leskauskaite Daiva , Pihlanto Anne , Inglingstad Ragnhild , Devold Tove Gulbrandsen , Vegarud Gerd Elisabeth , Birgisdottir Bryndis Eva , Gudjonsdottir Maria , Barile Daniela , Larsen Lotte Bach , Poulsen Nina Aagaard
Published: September 2021

Little is known about the extent of variation and activity of naturally occurring milk glycosidases and their potential to degrade milk glycans. A multi-omics approach was used to investigate the relationship between glycosidases and important bioactive compounds such as free oligosaccharides and O-linked glycans in bovine milk. Using 4-methylumbelliferone (4-MU) assays activities of eight indigenous glycosidases were determined, and by mass spectrometry and 1H NMR spectroscopy various substrates and metabolite products were quantified in a subset of milk samples from eight native North European cattle breeds. The results showed a clear variation in glycosidase activities among the native breeds. Interestingly, negative correlations between some glycosidases including β-galactosidase, N-acetyl-β-d-glucosaminidase, certain oligosaccharide isomers as well as O-linked glycans of κ-casein were revealed. Further, a positive correlation was found for free fucose content and α-fucosidase activity (r = 0.37, p-value < 0.001) indicating cleavage of fucosylated glycans in milk at room temperature. The results obtained suggest that milk glycosidases might partially degrade valuable glycans, which would result in lower recovery of glycans and thus represent a loss for the dairy ingredients industry if these activities are pronounced.
Retaining Geochemical Signatures during Aragonite-Calcite Transformation at Hydrothermal Conditions
Authors: Nguyen Anh , Gabitov Rinat , Jimenez Angel , Dygert Andrew , Varco Jac , Pérez-Huerta Alberto , Migdisov Artas , Paul Varun , Kirkland Brenda , Dash Padmanava
Published: September 2021

Transformation of aragonite, a mineral phase metastable at Earth’s surface, to calcite widely occurs in both sedimentary and metamorphic systems with the presence of an aqueous phase. The transformation process can affect geochemical signatures of aragonite (a protolith). This study focused on quantification of the retention of Mg/Ca and Sr/Ca ratios, and δ18O during the transformation process as well as evaluation of the transformation rate. To investigate the effect of transformation from aragonite to calcite on elemental and stable isotope ratios, we conducted a series of experiments in NaCl solutions at temperatures between 120 and 184 °C. Two additional experiments at 250 °C were conducted to estimate the transformation rate of aragonite to calcite. Protolith materials consist of (1) synthetic (Mg; Sr-bearing or non-Mg; Sr bearing) needle-shaped microcrystals of aragonite (<5 µm in size) and (2) larger chips (>100 µm in size) of natural aragonite. X-ray diffraction (XRD) showed that microcrystals successfully transformed to calcite within 30 h and scanning electron microscopy (SEM) yielded a change in the crystal size to >10 µm in rhombohedral shape. Electron backscatter diffraction (EBSD) of the larger aragonite chips showed that transformation to randomly oriented calcite occurred at the rims and along the cracks while the core retained an aragonite crystal structure. Isotope-ratio mass spectrometry (IRMS) analyses showed that calcite δ18O was controlled by temperature and δ18O of the solution. The obtained calibration curve of isotope fractionation factor versus temperature is consistent with other studies. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses showed that calcite partially or completely retained Mg/Ca and Sr/Ca ratios through the transformation.
Monitoring of Lithium Contents in Lithium Ores and Concentrate-Assessment Using X-ray Diffraction (XRD)
Authors: Pöllmann Herbert , König Uwe
Published: September 2021

Lithium plays an increasing role in battery applications, but is also used in ceramics and other chemical applications. Therefore, a higher demand can be expected for the coming years. Lithium occurs in nature mainly in different mineralizations but also in large salt lakes in dry areas. As lithium cannot normally be analyzed using XRF-techniques (XRF = X-ray Fluorescence), the element must be analyzed by time consuming wet chemical treatment techniques. This paper concentrates on XRD techniques for the quantitative analysis of lithium minerals and the resulting recalculation using additional statistical methods of the lithium contents. Many lithium containing ores and concentrates are rather simple in mineralogical composition and are often based on binary mineral assemblages. Using these compositions in binary and ternary mixtures of lithium minerals, such as spodumene, amblygonite, lepidolite, zinnwaldite, petalite and triphylite, a quantification of mineral content can be made. The recalculation of lithium content from quantitative mineralogical analysis leads to a fast and reliable lithium determination in the ores and concentrates. The techniques used for the characterization were quantitative mineralogy by the Rietveld method for determining the quantitative mineral compositions and statistical calculations using additional methods such as partial least square regression (PLSR) and cluster analysis methods to predict additional parameters, like quality, of the samples. The statistical calculations and calibration techniques makes it especially possible to quantify reliable and fast. Samples and concentrates from different lithium deposits and occurrences around the world were used for these investigations. Using the proposed XRD method, detection limits of less than 1% of mineral and, therefore down to 0.1% lithium oxide, can be reached. Case studies from a hard rock lithium deposit will demonstrate the value of mineralogical monitoring during mining and the different processing steps. Additional, more complex considerations for the analysis of lithium samples from salt lake brines are included and will be discussed.
A Case Study of Rock Type Prediction Using Random Forests: Erdenet Copper Mine, Mongolia
Authors: Sarantsatsral Narmandakh , Ganguli Rajive , Pothina Rambabu , Tumen-Ayush Batmunkh
Published: September 2021

In a mine, knowledge of rock types is often desired as they are important indicators of grade, mineral processing complications, or geotechnical attributes. It is common to model the rock types with visual graphics tools using geologist-generated rock type information in exploration drillhole databases. Instead of this manual approach, this paper used random forest (RF), a machine learning (ML) algorithm, to model the rock type at Erdenet Copper Mine, Mongolia. Exploration drillhole data was used to develop the RF models and predict the rock type based on the coordinates of locations. Data selection and model evaluation methods were designed to ensure applicability for real life scenarios. In the scenario where rock type is predicted close to locations where information is available (such as in blocks being blasted), RF did very well with an overall success rate (OSR) of 89%. In the scenario where rock type was predicted for two future benches (i.e., 30 m below known locations), the best OSR was 86%. When an exploration program was simulated, performance was poor with a OSR of 59%. The results indicate that EMC can leverage RF models for short-term and long-term planning by predicting rock types within drilling blocks or future blocks quite accurately.
Chemically Oscillating Reactions during the Diagenetic Formation of Ediacaran Siliceous and Carbonate Botryoids
Authors: Papineau Dominic , Yin Jiayu , Devine Kevin G. , Liu Deng , She Zhenbing
Published: September 2021

Chemically oscillating reactions are abiotic reactions that produce characteristic, periodic patterns during the oxidation of carboxylic acids. They have been proposed to occur during the early diagenesis of sediments that contain organic matter and to partly explain the patterns of some enigmatic spheroids in malachite, phosphorite, jasper chert, and stromatolitic chert from the rock record. In this work, circularly concentric self-similar patterns are shown to form in new chemically oscillating reaction experiments with variable mixtures of carboxylic acids and colloidal silica. This is carried out to best simulate in vitro the diagenetic formation of botryoidal quartz and carbonate in two Ediacaran-age geological formations deposited after the Marinoan–Nantuo snowball Earth event in South China. Experiments performed with alkaline colloidal silica (pH of 12) show that this compound directly participates in pattern formation, whereas those with humic acid particles did not. These experiments are particularly noteworthy since they show that pattern formation is not inhibited by strong pH gradients, since the classical Belousov–Zhabotinsky reaction occurs in solution with a pH around 2. Our documentation of hundreds of classical Belousov–Zhabotinsky experiments yields a number of self-similar patterns akin to those in concretionary structures after the Marinoan–Nantuo snowball Earth event. Morphological, compositional, and size dimensional comparisons are thus established between patterns from these experiments and in botryoidal quartz and carbonate from the Doushantuo and Denying formations. Selected specimens exhibit circularly concentric layers and disseminations of organic matter in quartz and carbonate, which also occurs in association with sub-micron-size pyrite and sub-millimetre iron oxides within these patterns. X-ray absorption near edge structure (XANES) analyses of organic matter extracted from dolomite concretions in slightly younger, early Cambrian Niutitang Formation reveal the presence of carboxylic and N-bearing molecular functional groups. Such mineral assemblages, patterns, and compositions collectively suggest that diagenetic redox reactions take place during the abiotic decay of biomass, and that they involve Fe, sulphate, and organic matter, similarly to the pattern-forming experiments. It is concluded that chemically oscillating reactions are at least partly responsible for the formation of diagenetic siliceous spheroids and concretionary carbonate, which can relate to various other persistent problems in Earth and planetary sciences.
Simultaneous Quantification of 25 Fentanyl Derivatives and Metabolites in Oral Fluid by Means of Microextraction on Packed Sorbent and LC–HRMS/MS Analysis
Authors: Vincenti Flaminia , Montesano Camilla , Pirau Svetlana , Gregori Adolfo , Di Rosa Fabiana , Curini Roberta , Sergi Manuel
Published: September 2021

Fentanyl and fentalogs’ intake as drugs of abuse is experiencing a great increase in recent years. For this reason, there are more and more cases in which it is important to recognize and quantify these molecules and related metabolites in biological matrices. Oral fluid (OF) is often used to find out if a subject has recently used a psychoactive substance and if, therefore, the person is still under the effect of psychotropics. Given its difficulty in handling, good sample preparation and the development of instrumental methods for analysis are essential. In this work, an analytical method is proposed for the simultaneous determination of 25 analytes, including fentanyl, several derivatives and metabolites. OF was collected by means of passive drool; sample pretreatment was developed in order to be fast, simple and possibly semi-automated by exploiting microextraction on packed sorbent (MEPS). The analysis was performed by means of LC–HRMS/MS obtaining good identification and quantification of all the analytes in less than 10 min. The proposed method was fully validated according to the Scientific Working Group for Forensic Toxicology (SWGTOX) international guidelines. Good results were obtained in terms of recoveries, matrix effect and sensitivity, showing that this method could represent a useful tool in forensic toxicology. The presented method was successfully applied to the analysis of proficiency test samples.
Structural Transformation and Creativity Induced by Biological Agents during Fermentation of Edible Nuts from Terminalia catappa
Authors: Odutayo Oluwatofunmi E. , Adegboye Bose E. , Omonigbehin Emmanuel A. , Olawole Tolulope D. , Ogunlana Olubanke O. , Afolabi Israel S.
Published: September 2021

Terminalia catappa L. (tropical almond) is a nutritious fruit found mainly in the tropics. This study is aimed to establish the naturally biotransformed molecules and identify the probiotic agents facilitating the fermentation. The aqueous extracts from both the unfermented and fermented T. catappa nuts were subjected to gas chromatography/mass spectrometry (GC/MS) analysis. Syringol (6.03%), glutamine (1.71%), methyl laurate (1.79%), methyl palmitate (1.53%), palmitic acid (5.20%), palmitoleic acid (2.80%), and methyl oleate (2.97%) were detected in the unfermented nuts of the T. catappa. Additionally, two of these natural compounds (palmitic acid (4.19%) and palmitoleic acid (1.48%)) survived the fermentation process to emerge in the fermented seeds. The other natural compounds were biotransformed into 2,3-butanediol (1.81%), butyric acid (16.20%), propane-1,3-diol (19.66%), neoheptanol (2.89%), 2-piperidinone (6.63%), palmitoleic acid (1.18%), formamide, n-(p-hydroxyphenethyl)- (2.80%), and cis-vaccenic acid (1.69%) that newly emerged in the fermented seeds. The phytochemical compounds are likely carbon sources for the organisms facilitating the biotransformed molecules and product production. Four (4) potential probiotic bacteria strains, namely, Probt B1a, Probt B2a, Probt B4a, and Probt B4b, were isolated from the fermented nut. Enterococcus faecum, and Enterococcus faecalis were the organisms identified as driving the fermentation of the seeds. All strains were gram-positive, catalase-negative, and non-hemolytic, which suggests their harmless nature. N-(p-hydroxyphenethyl)-) was associated with fermentation for the first time, and neoheptanol was discovered as the main alcoholic molecule formed during the fermentation of the seeds. This fermentation is a handy tool for bio-transforming compounds in raw food sources into compounds with nutritious and therapeutic potentials.
Crystal Structure and Solid-State Packing of 4-Chloro-5H-1,2,3-dithiazol-5-one and 4-Chloro-5H-1,2,3-dithiazole-5-thione
Authors: Constantinides Christos P. , Koyioni Maria , Bazzi Fadwat , Manoli Maria , Lawson Daniel B. , Koutentis Panayiotis A.
Published: September 2021

The crystal structure and solid-state packing of 4-chloro-5H-1,2,3-dithiazol-5-one and two polymorphs of 4-chloro-5H-1,2,3-dithiazole-5-thione were analyzed and compared to structural data of similar systems. These five-membered S,N-rich heterocycles are planar with considerable bond localization. All three structures demonstrate tight solid-state packing without voids which is attributed to a rich network of short intermolecular electrostatic contacts. These include Sδ+…Nδ−, Sδ+…Oδ−, Sδ+…Clδ− and Sδ+…Sδ− interactions that are well within the sum of their van der Waals radii (∑VDW). B3LYP, BLYP, M06, mPW1PW, PBE and MP2 were employed to calculate their intramolecular geometrical parameters, the Fukui condensed functions to probe their reactivity, the bond order, Bird Index and NICS(1) to establish their aromaticity.
On the Interactions of Melatonin/β-Cyclodextrin Inclusion Complex: A Novel Approach Combining Efficient Semiempirical Extended Tight-Binding (xTB) Results with Ab Initio Methods
Authors: Ferrero Riccardo , Pantaleone Stefano , Delle Piane Massimo , Caldera Fabrizio , Corno Marta , Trotta Francesco , Brunella Valentina
Published: September 2021

Melatonin (MT) is a molecule of paramount importance in all living organisms, due to its presence in many biological activities, such as circadian (sleep–wake cycle) and seasonal rhythms (reproduction, fattening, molting, etc.). Unfortunately, it suffers from poor solubility and, to be used as a drug, an appropriate transport vehicle has to be developed, in order to optimize its release in the human tissues. As a possible drug-delivery system, β-cyclodextrin (βCD) represents a promising scaffold which can encapsulate the melatonin, releasing when needed. In this work, we present a computational study supported by experimental IR spectra on inclusion MT/βCD complexes. The aim is to provide a robust, accurate and, at the same time, low-cost methodology to investigate these inclusion complexes both with static and dynamic simulations, in order to study the main actors that drive the interactions of melatonin with β-cyclodextrin and, therefore, to understand its release mechanism.
Photoredox-Catalyzed Reduction of Halogenated Arenes in Water by Amphiphilic Polymeric Nanoparticles
Authors: Eisenreich Fabian , Kuster Tom H. R. , van Krimpen David , Palmans Anja R. A.
Published: September 2021

The use of organic photoredox catalysts provides new ways to perform metal-free reactions controlled by light. While these reactions are usually performed in organic media, the application of these catalysts at ambient temperatures in aqueous media is of considerable interest. We here compare the activity of two established organic photoredox catalysts, one based on 10-phenylphenothiazine (PTH) and one based on an acridinium dye (ACR), in the light-activated dehalogenation of aromatic halides in pure water. Both PTH and ACR were covalently attached to amphiphilic polymers that are designed to form polymeric nanoparticles with hydrodynamic diameter DH ranging between 5 and 11 nm in aqueous solution. Due to the hydrophobic side groups that furnish the interior of these nanoparticles after hydrophobic collapse, water-insoluble reagents can gather within the nanoparticles at high local catalyst and substrate concentrations. We evaluated six different amphiphilic polymeric nanoparticles to assess the effect of polymer length, catalyst loading and nature of the catalyst (PTH or ACR) in the dechlorination of a range of aromatic chlorides. In addition, we investigate the selectivity of both catalysts for reducing different types of aryl-halogen bonds present in one molecule, as well as the activity of the catalysts for C-C cross-coupling reactions. We find that all polymer-based catalysts show high activity for the reduction of electron-poor aromatic compounds. For electron-rich compounds, the ACR-based catalyst is more effective than PTH. In the selective dehalogenation reactions, the order of bond stability is C-Cl > C-Br > C-I irrespective of the catalyst applied. All in all, both water-compatible systems show good activity in water, with ACR-based catalysts being slightly more efficient for more resilient substrates.
The Synthesis of Blood Group Antigenic A Trisaccharide and Its Biotinylated Derivative
Authors: Kazakova Ekaterina D. , Yashunsky Dmitry V. , Nifantiev Nikolay E.
Published: September 2021

Blood group antigenic A trisaccharide represents the terminal residue of all A blood group antigens and plays a key role in blood cell recognition and blood group compatibility. Herein, we describe the synthesis of the spacered A trisaccharide by means of an assembly scheme that employs in its most complex step the recently proposed glycosyl donor of the 2-azido-2-deoxy-selenogalactoside type, bearing stereocontrolling 3-O-benzoyl and 4,6-O-(di-tert-butylsilylene)-protecting groups. Its application provided efficient and stereoselective formation of the required α-glycosylation product, which was then deprotected and subjected to spacer biotinylation to give both target products, which are in demand for biochemical studies.
Enhancement of the Anti-Stokes Fluorescence of Hollow Spherical Carbon Nitride Nanostructures by High Intensity Green Laser
Authors: Zinin Pavel V. , Acosta-Maeda Tayro E. , Misra Anupam K. , Sharma Shiv K.
Published: September 2021

Fluorescence spectra of graphitic (g-C3N4) and spherical (s-C3N4) modifications of carbon nitride were measured as a function of green pulsed (6 ns-pulse) laser intensity. It was found that the intensity of the laser increases the maximum of the fluorescence shifts towards the anti-Stokes side of the fluorescence for s-C3N4 spherical nanoparticles. This phenomenon was not observed for g-C3N4 particles. The maximum of the anti-Stokes fluorescence in s-C3N4 nanoparticles was observed at 480 nm. The ratio of the intensity of the anti-Stokes peak (centered at 480 nm) to that of the Stokes peak (centered at 582 nm) was measured to be I484/582 = 6.4 × 10−3 at a low level of intensity (5 mW) of a green pulsed laser, whereas it rose to I484/582 = 2.27 with a high level of laser intensity (1500 mW).
Scalable Sacrificial Templating to Increase Porosity and Platinum Utilisation in Graphene-Based Polymer Electrolyte Fuel Cell Electrodes
Authors: Suter Theo A. M. , Clancy Adam J. , Rubio Carrero Noelia , Heitzmann Marie , Guetaz Laure , Shearing Paul R. , Mattevi Cecilia , Gebel Gérard , Howard Christopher A. , Shaffer Milo S. P. , McMillan Paul F. , Brett Dan J. L.
Published: September 2021

Polymer electrolyte fuel cells hold great promise for a range of applications but require advances in durability for widespread commercial uptake. Corrosion of the carbon support is one of the main degradation pathways; hence, corrosion-resilient graphene has been widely suggested as an alternative to traditional carbon black. However, the performance of bulk graphene-based electrodes is typically lower than that of commercial carbon black due to their stacking effects. This article reports a simple, scalable and non-destructive method through which the pore structure and platinum utilisation of graphene-based membrane electrode assemblies can be significantly improved. Urea is incorporated into the catalyst ink before deposition, and is then simply removed from the catalyst layer after spraying by submerging the electrode in water. This additive hinders graphene restacking and increases porosity, resulting in a significant increase in Pt utilisation and current density. This technique does not require harsh template etching and it represents a pathway to significantly improve graphene-based electrodes by introducing hierarchical porosity using scalable liquid processes.
Stable, Ductile and Strong Ultrafine HT-9 Steels via Large Strain Machining
Authors: El-Atwani Osman , Kim Hyosim , Gigax Jonathan G. , Harvey Cayla , Aytuna Berk , Efe Mert , Maloy Stuart A.
Published: September 2021

Beyond the current commercial materials, refining the grain size is among the proposed strategies to manufacture resilient materials for industrial applications demanding high resistance to severe environments. Here, large strain machining (LSM) was used to manufacture nanostructured HT-9 steel with enhanced thermal stability, mechanical properties, and ductility. Nanocrystalline HT-9 steels with different aspect rations are achieved. In-situ transmission electron microscopy annealing experiments demonstrated that the nanocrystalline grains have excellent thermal stability up to 700 °C with no additional elemental segregation on the grain boundaries other than the initial carbides, attributing the thermal stability of the LSM materials to the low dislocation densities and strains in the final microstructure. Nano-indentation and micro-tensile testing performed on the LSM material pre- and post-annealing demonstrated the possibility of tuning the material’s strength and ductility. The results expound on the possibility of manufacturing controlled nanocrystalline materials via a scalable and cost-effective method, albeit with additional fundamental understanding of the resultant morphology dependence on the LSM conditions.
Biocompatible Silver Nanoparticles: Study of the Chemical and Molecular Structure, and the Ability to Interact with Cadmium and Arsenic in Water and Biological Properties
Authors: Bertelà Federica , Marsotto Martina , Meneghini Cecilia , Burratti Luca , Maraloiu Valentin-Adrian , Iucci Giovanna , Venditti Iole , Prosposito Paolo , D’Ezio Veronica , Persichini Tiziana , Battocchio Chiara
Published: September 2021

In the field of research for designing and preparing innovative nanostructured systems, these systems are able to reveal the presence of heavy metals in water samples, and can efficiently and selectively interact with them, allowing for future applications in the field of water remediation. We investigated the electronic and molecular structure, as well as the morphology, of silver nanoparticles stabilized by mixed biocompatible ligands (the amino acid L-cysteine and the organic molecule citrate) in the presence of cadmium and arsenic ions. The molecular, electronic, and local structure at the ligands/silver nanoparticles interface was probed by the complementary synchrotron radiation-induced techniques (SR-XPS, NEXAFS and XAS). The optical absorption (in the UV-Vis range) of the nanosystem was investigated in the presence of Cd(II) and As(III) and the observed behavior suggested a selective interaction with cadmium. In addition, the toxicological profile of the innovative nanosystem was assessed in vitro using a human epithelial cell line HEK293T. We analyzed the viability of the cells treated with silver nanoparticles, as well as the activation of antioxidant response.
Visible-Light Active Sulfur-Doped Titania Nanoparticles Immobilized on a Silica Matrix: Synthesis, Characterization and Photocatalytic Degradation of Pollutants
Authors: Kalampaliki Theodora , Makri Sofia P. , Papadaki Evanthia , Grigoropoulos Alexios , Zoikis Karathanasis Alexandros , Deligkiozi Ioanna
Published: September 2021

The photocatalytic oxidation (PCO) of pollutants using TiO2-based materials can significantly improve indoor air quality (IAQ), which in turn, has a significant impact on human health and life expectancy. TiO2-based nanoparticles (NPs) are widely used as part of building materials to function as photocatalysts in PCO. In this work, a series of sulfur-doped TiO2 NPs immobilized on a silica matrix were synthesized by combining a sol-gel process with ball milling. The samples were structurally characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), Fourier-transform infrared spectroscopy (FT-IR) and N2 adsorption-desorption isotherms. Furthermore, the morphological characteristics were determined by dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The photocatalytic activity of the as prepared S-doped TiO2/SiO2 NPs in the degradation of liquid and air pollutants under visible-light irradiation was investigated. Our results show that sulfur is an effective dopant for activating TiO2/SiO2 photocatalysts under visible-light irradiation. Silica constitutes a “safe-by-design” approach and inhibits the aggregation of NPs during synthesis. The most efficient photocatalyst afforded 79% removal of methyl orange (5 h), 26% removal of acetaldehyde (1 h) and 12% oxidation of NO (1 h).
Robust Biomimetic Nacreous Aramid Nanofiber Composite Films with Ultrahigh Thermal Conductivity by Introducing Graphene Oxide and Edge-Hydroxylated Boron Nitride Nanosheet
Authors: Xu Cenkai , Wei Chengmei , Li Qihan , Li Zihan , Zhang Zongxi , Ren Junwen
Published: September 2021

Dielectric materials with excellent thermally conductive and mechanical properties can enable disruptive performance enhancement in the areas of advanced electronics and high-power devices. However, simultaneously achieving high thermal conductivity and mechanical strength for a single material remains a challenge. Herein, we report a new strategy for preparing mechanically strong and thermally conductive composite films by combining aramid nanofibers (ANFs) with graphene oxide (GO) and edge-hydroxylated boron nitride nanosheet (BNNS-OH) via a vacuum-assisted filtration and hot-pressing technique. The obtained ANF/GO/BNNS film exhibits an ultrahigh in-plane thermal conductivity of 33.4 Wm−1 K−1 at the loading of 10 wt.% GO and 50 wt.% BNNS-OH, which is 2080% higher than that of pure ANF film. The exceptional thermal conductivity results from the biomimetic nacreous “brick-and-mortar” layered structure of the composite film, in which favorable contacting and overlapping between the BNNS-OH and GO is generated, resulting in tightly packed thermal conduction networks. In addition, an outstanding tensile strength of 93.3 MPa is achieved for the composite film, owing to the special biomimetic nacreous structure as well as the strong π−π interactions and extensive hydrogen bonding between the GO and ANFs framework. Meanwhile, the obtained composite film displays excellent thermostability (Td = 555 °C, Tg > 400 °C) and electrical insulation (4.2 × 1014 Ω·cm). We believe that these findings shed some light on the design and fabrication of multifunctional materials for thermal management applications.
Relationship among Nutritional Intake, Anxiety, and Menstrual Irregularity in Elite Rowers
Authors: Miyamoto Mana , Hanatani Yuko , Shibuya Kenichi
Published: September 2021

There is evidence showing that excessive mental stress is detrimental to the menstrual period, and it is known that many elite athletes are highly susceptible to mental anxiety. This study investigated the nutritional intake and mental anxiety of 104 relatively young elite endurance athletes aged 16 to 23 years and used a multiple logistic model to examine the factors that might be related to menstrual irregularity. Calcium intake was marginally associated with the occurrence of menstrual irregularities (odds ratio = 1.004, p = 0.030), whereas there were strong associations between body mass or state anxiety and menstrual irregularities in elite athletes (odds ratio = 0.557, p = 0.035 for body mass; odds ratio = 1.094, p = 0.006 for state anxiety). These results suggested that state anxiety would be an important factor causing menstrual irregularity in elite endurance athletes. It is recommended that elite athletes are monitored for anxiety levels and develop a strategy for stress management.
It Is about Quality, Not the Badge: A Response to Is the Ph.D. Well for Nursing Faculty Running Dry?
Authors: Jones Martin , Bone Alison , Heffernan Julia
Published: September 2021

We read with interest the editorial by Watson et al [...]