bluuebunny/crossref_metadata_2025 huggingface dataset:
PTFE-Carbon Nanotubes and Lipase B from Candida antarctica—Long-Lasting Marriage for Ultra-Fast and Fully Selective Synthesis of Levulinate Esters
Authors: Szelwicka Anna , Siewniak Agnieszka , Kolanowska Anna , Boncel Sławomir , Chrobok Anna
Published: March 2021

An effective method for levulinic acid esters synthesis by the enzymatic Fischer esterification of levulinic acid using a lipase B from Candida antarctica (CALB) immobilized on the advanced material consisting of multi-wall carbon nanotubes (MWCNTs) and a hydrophobic polymer—polytetrafluoroethylene (Teflon, PTFE)—as a heterogeneous biocatalyst, was developed. An active phase of the biocatalyst was obtained by immobilization via interfacial activation on the surface of the hybrid material MWCNTs/PTFE (immobilization yield: 6%, activity of CALB: 5000 U∙L∙kg−1, enzyme loading: 22.5 wt.%). The catalytic activity of the obtained biocatalyst and the effects of the selected reaction parameters, including the agitation speed, the amount of PTFE in the CALB/MWCNT-PTFE biocatalyst, the amount of CALB/MWCNT-PTFE, the type of organic solvent, n-butanol excess, were tested in the esterification of levulinic acid by n-butanol. The results showed that the use of a two-fold excess of levulinic acid to n-butanol, 22.5 wt.% of CALB on MWCNT-PTFE (0.10 wt.%) and cyclohexane as a solvent at 20 °C allowed one to obtain n-butyl levulinate with a high yield (99%) and selectivity (>99%) after 45 min. The catalyst retained its activity and stability after three cycles, and then started to lose activity until dropping to a 69% yield of ester in the sixth reaction run. The presented method has opened the new possibilities for environmentally friendly synthesis of levulinate esters.
A Simple Method for a Protective Coating on Stainless Steel against Molten Aluminum Alloy Comprising Polymer-Derived Ceramics, Oxides and Refractory Ceramics
Authors: Quenard Sébastien , Roumanie Marilyne
Published: March 2021

A new coating based on polymer-derived ceramics (PDC), oxides and refractory ceramic with a thickness of around 50 µm has been developed to improve the resistance corrosion of stainless steel substrate against molten aluminum alloy in a thermal energy storage (TES) system designed to run at high temperature (up to 600 °C). These coatings implemented by straightforward methods, like tape casting or paintbrush, were coated on planar and cylindrical stainless-steel substrates, pyrolyzed at 700 °C before being plunged for 600 and 1200 h in molten AlSi12 at 700 °C. The stainless-steel substrate appears healthy without intermetallic compounds, characteristic of molten aluminum alloy corrosion. The protective coating against AlSi12 corrosion shows excellent performance and appears interesting for TES applications.
Regular-Type Liesegang Pattern of AgCl in a One-Dimensional System
Authors: Sakamoto Shun , Itatani Masaki , Tsukada Kanta , Nabika Hideki
Published: March 2021

The Liesegang phenomenon can be used for micro- and nanofabrication processes to yield materials with periodic precipitation of diverse types of materials. Although there have been several attempts to control the periodicity of the Liesegang patterns, it remains unclear whether the periodic precipitation of AgCl in gel medium causes regular- or revert-type patterns. To confirm the periodicity of the AgCl pattern, we conduct one-dimensional experiments under various ion concentration conditions. From microscopic observations, three different precipitation modes were observed, i.e., continuous precipitation with a sharp front, periodic precipitation and continuous precipitation with a gradual front. For these three modes, numerical analyses of the pattern geometry are performed for the periodic precipitation. It was confirmed that the regular-type pattern appeared for all concentration conditions conducted in the present experiments. Furthermore, the pattern was found to obey the spacing law and the Matalon–Packter law. From our experiments, we concluded that AgCl forms regular-type Liesegang patterns, regardless of the dimension of diffusion.
Mechanical and Thermal Properties of Polyurethane Materials and Inflated Insulation Chambers
Authors: Čubrić Goran , Salopek Čubrić Ivana , Rogale Dubravko , Firšt Rogale Snježana
Published: March 2021

Evaluating mechanical and thermal characteristics of garment systems or their segments is important in an attempt to provide optimal or at least satisfying levels of comfort and safety, especially in the cold environment. The target groups of users may be athletes engaged in typical sports that are trained in the cold, as well as football players that play matches and train outdoors during the winter season. Previous studies indicated an option to substitute the inner layers of an intelligent garment with polyurethane inflated chambers (PIC) to increase and regulate thermal insulation. In this paper, the authors investigate the mechanical properties of polyurethane material with and without ultrasonic joints. Furthermore, they investigate the potential of designed PICs in terms of efficiency and interdependence of air pressure and heat resistance. The results indicated that an inflated PIC with four diagonal ultrasonic joints has the highest ability to maintain the optimal thermal properties of an intelligent clothing system. The influence of direction and number of ultrasonic joints on the mechanical properties of polyurethane material is confirmed, especially in terms of compression resilience and tensile energy.
Influence of Cr3C2 and VC Content on WC Grain Size, WC Shape and Mechanical Properties of WC–6.0 wt. % Co Cemented Carbides
Authors: Yin Chao , Peng Yingbiao , Ruan Jianming , Zhao Lin , Zhang Ren , Du Yong
Published: March 2021

In this paper, the influences of Cr3C2/VC content on WC grain size, WC grain shape and mechanical properties of WC–6 wt. % Co cemented carbides were investigated. The results showed that the grain size first rapidly decreased and then slightly decreased with the increasing Cr3C2/VC content, and VC led to finer grain size and narrower size distribution. HRTEM/EDS analysis of the WC/Co interface indicates that the segregation concentration of V is much larger than that of Cr, which may be a strong response to the higher inhibition efficiency of VC. The addition of Cr3C2 induced triangular prism shape WC grains while VC generated stepped triangular prism grains. Despite the grain growth inhibitor (GGI) mechanisms of Cr3C2/VC have been extensively studied in the literature, the doping amount, especially the doping limit, has not been systematically investigated. In this work, the saturated solubilities of Cr and V in cobalt binder phase along with carbon content hare been predicted based on thermodynamic calculations. Based on the theoretical calculations, the doping amount of Cr3C2/VC is designed to be gradually increasing until more or less over their maximum solubilities in the binder phase, thereby investigating the subsequent microstructure and mechanical properties. When the doping of Cr3C2/VC exceeds the maximum solubility in Co phase, Co-rich Cr-carbides and Co-deficient V-carbides would form respectively, which were detrimental to the transverse rupture strength (TRS) and impact toughness. The hardness increased with the increasing Cr3C2/VC content, while the fracture toughness decreased with the increasing Cr3C2/VC content. The TRS initially enhanced and then declined, but the stepped triangular prism shape grains and low fraction of WC/Co interface in WC–6Co–VC cemented carbide led to a more pronounced decline in the TRS. The sample with 0.6 wt. % Cr3C2 addition had good comprehensive mechanical properties, its hardness, fracture toughness and TRS were 1880 kg/mm2, 9.32 MPa·m1/2 and 3450 MPa, respectively.
Mechanical Pull-Out Test of a New Hybrid Fixture-Abutment Connection: An In Vitro Study
Authors: D’Addazio Gianmaria , Sinjari Bruna , Arcuri Lorenzo , Femminella Beatrice , Murmura Giovanna , Santilli Manlio , Caputi Sergio
Published: March 2021

Implant abutment connection was described among the main causes of peri-implant bone resorption. The aim of this in vitro study was to test the coupling capacity, the surface modification of a new hybrid connection and the influence of repeated connection activations caused during the main clinical and laboratory phases. A total of 40 implant-abutment screw retained systems with 10°-conical and internal hexagon connection were tested. The connection was screwed, fixed to the universal test machine, removed the screw and a pull-out test was performed. Test was repeated five times in succession. Also Scanning Electron Microscopy (SEM) was used to detect microscopically surface modification. Analysis of variance and Tukey tests were used for the statistical analysis. Pull-out test reveals a mean value of 131.35 ± 16.52 Newton Centimeter (N·cm). For each single activation, results from first to fifth were: 113.9 ± 13.02, 126.1 ± 12.81, 138.11 ± 15.15, 138.8 ± 11.90 and 140 ± 12.99 N·cm. A statistically significant difference between the measurements and an increase in the removal force was shown. The collected data supports the use of this new type of connection, resulting in a very strong interface between implant and abutment. Also, repeated activation of connection can promote a better coupling of the implant-abutment interface.
The Effect of Quenching and Partitioning (Q&P) Heat Treatment on the Microstructure and Mechanical Properties of High Boron Steel
Authors: Li Zhao , Wu Run , Li Mingwei , Zeng Song-Sheng , Wang Yu , Xie Tian , Wu Teng
Published: March 2021

High boron steel is prone to brittle failure due to the boride distributed in it with net-like or fishbone morphology, which limit its applications. The Quenching and Partitioning (Q&P) heat treatment is a promising process to produce martensitic steel with excellent mechanical properties, especially high toughness by increasing the volume fraction of retained austensite (RA) in the martensitic matrix. In this work, the Q&P heat treatment is used to improve the inherent defect of insufficient toughness of high boron steel, and the effect mechanism of this process on microstructure transformation and the change of mechanical properties of the steel has also been investigated. The high boron steel as-casted is composed of martensite, retained austensite (RA) and eutectic borides. A proper quenching and partitioning heat treatment leads to a significant change of the microstructure and mechanical properties of the steel. The net-like and fishbone-like boride is partially broken and spheroidized. The volume fraction of RA increases from 10% in the as-cast condition to 19%, and its morphology also changes from blocky to film-like. Although the macro-hardness has slightly reduced, the toughness is significantly increased up to 7.5 J·cm−2, and the wear resistance is also improved.
Cyclic Deformation Induced Residual Stress Evolution and 3D Short Fatigue Crack Growth Investigated by Advanced Synchrotron Tomography Techniques
Authors: Dönges Benjamin , Syha Melanie , Hüsecken Anne K. , Pietsch Ullrich , Ludwig Wolfgang , Krupp Ulrich , Christ Hans-Jürgen
Published: March 2021

Diffraction and phase contrast tomography techniques were successfully applied to an austenitic–ferritic duplex stainless steel representing exemplarily a metallic material containing two phases with different crystal structures. The reconstructed volumes of both phases were discretized by finite elements. A crystal plasticity finite-element analysis was executed in order to simulate the development of the experimentally determined first and second order residual stresses, which built up due to the manufacturing process of the material. Cyclic deformation simulations showed the single-grain-resolved evolution of initial residual stresses in both phases and were found to be in good agreement with the experimental results. Solely in ferritic grains, residual stresses built up due to cyclic deformation, which promoted crack nucleation in this phase. Furthermore, phase contrast tomography was applied in order to analyze the mechanisms of fatigue crack nucleation and short fatigue crack propagation three-dimensionally and nondestructively. The results clearly showed the significance of microstructural barriers for short fatigue crack growth at the surface, as well as into the material. The investigation presented aims for a better understanding of the three-dimensional mechanisms governing short fatigue crack propagation and, in particular, the effect of residual stresses on these mechanisms. The final goal was to generate tailored microstructures for improved fatigue resistance and enhanced fatigue life.
On the Possibility of Generalizing the Results of Studies of Dynamical Systems on the Example of a Vehicle Suspension
Authors: Dubrovskiy Anatoliy , Aliukov Sergei , Osintsev Konstantin
Published: March 2021

The dynamics of mechanical systems, the operation of electromagnetic and electronic devices and devices, the principle of operation of a number of machines and mechanisms, engineering structures from various fields are often described by differential equations and their systems. Differential equations are often mathematical models of the movement and operation of various engineering objects. As a rule, such equations are solved by numerical methods for specific parameter values. These methods of solving differential equations are widely used in practice. However, these methods also have significant disadvantages. For example, the solution of differential equations is obtained for a specific object with the specified parameters. In this case, a solution is obtained for a single point in the parameter space of a set of similar objects, points in this space of the considered family of objects. A natural question arises: Is it possible to extend the results of the solution for a single point in space (a specific object) and the identified properties and regularities to other points (other objects) of the considered family? The purpose of this article is to identify conditions under which it is possible to generalize the results of solving differential equations with specific parameter values describing a single construction to the entire family of similar constructions, the entire space of parameters under consideration. The implementation of the identified conditions is illustrated by the example of solving the problem of “analyzing the dynamic properties of a mathematical model of a car with adaptive (adjustable) suspension of a new principle of action (developed by the authors), moving at a variable speed along an indirect profile of the road surface and developing recommendations for their radical improvement”.
Compartmental Learning versus Joint Learning in Engineering Education
Authors: Santos María Jesús , Medina Alejandro , Mateos Roco José Miguel , Queiruga-Dios Araceli
Published: March 2021

Sophomore students from the Chemical Engineering undergraduate Degree at the University of Salamanca are involved in a Mathematics course during the third semester and in an Engineering Thermodynamics course during the fourth one. When they participate in the latter they are already familiar with mathematical software and mathematical concepts about numerical methods, including non-linear equations, interpolation or differential equations. We have focused this study on the way engineering students learn Mathematics and Engineering Thermodynamics. As students use to learn each matter separately and do not associate Mathematics and Physics, they separate each matter into different and independent compartments. We have proposed an experience to increase the interrelationship between different subjects, to promote transversal skills, and to make the subjects closer to real work. The satisfactory results of the experience are exposed in this work. Moreover, we have analyzed the results obtained in both courses during the academic year 2018–2019. We found that there is a relation between both courses and student’s final marks do not depend on the course.
Repdigits as Product of Terms of k-Bonacci Sequences
Authors: Coufal Petr , Trojovský Pavel
Published: March 2021

For any integer k≥2, the sequence of the k-generalized Fibonacci numbers (or k-bonacci numbers) is defined by the k initial values F−(k−2)(k)=⋯=F0(k)=0 and F1(k)=1 and such that each term afterwards is the sum of the k preceding ones. In this paper, we search for repdigits (i.e., a number whose decimal expansion is of the form aa…a, with a∈[1,9]) in the sequence (Fn(k)Fn(k+m))n, for m∈[1,9]. This result generalizes a recent work of Bednařík and Trojovská (the case in which (k,m)=(2,1)). Our main tools are the transcendental method (for Diophantine equations) together with the theory of continued fractions (reduction method).
Does the Severity of Obstructive Sleep Apnea Have an Independent Impact on Systemic Inflammation?
Authors: Suša Romana , Ćupurdija Vojislav , Novković Ljiljana , Ratinac Miloš , Janković Slobodan , Đoković Danijela , Jovanović Jovan , Pantić Katarina , Simović Stefan , Bazić-Sretenović Danijela , Čekerevac Ivan
Published: March 2021

Background and Objectives: This paper aims to show whether obstructive sleep apnea (OSA) severity increases the level of systemic inflammation markers regardless of body mass index (BMI) and body composition. Materials and Methods: In total, 128 patients with OSA were included in the study. Examinees were divided into two groups: one with mild OSA (apnea–hypopnea index (AHI) < 15) and one with moderate and severe OSA (AHI ≥ 15). Nutritional status was assessed using body mass index, body composition by dual X-ray absorptiometry. Systemic inflammation was assessed on the basis of plasma concentrations of tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6), and serum level of C-reactive protein (CRP). Results: We found elevated mean values of the evaluated systemic inflammation markers (CRP, TNF-α, IL-6) in a group with AHI ≥ 15, although there was no statistical significance. Our research found a significant positive correlation with BMI (r = 0.633, p < 0.001), as well as with body fat percentage (r = 0.450, p = 0.024) and serum CRP values. Significant correlation was found between the plasma IL-6 concentration and body fat percentage (FM%) (r = 0.579, p = 0.003) and lean body mass (r = −0.501, p = 0.013). Multivariate regression analysis did not show any independent predictor (parameters of OSA, nutritional status, body composition) of the systemic inflammation markers. Conclusions: Neither one tested parameter (nutritional status and body composition) of the severity of OSA was identified as an independent prognostic factor for the severity of systemic inflammation in patients with OSA.
The Most Common Lesions Detected by Neuroimaging as Causes of Epilepsy
Authors: Adamczyk Bożena , Węgrzyn Karolina , Wilczyński Tomasz , Maciarz Justyna , Morawiec Natalia , Adamczyk-Sowa Monika
Published: March 2021

Epilepsy is a common neurological disorder characterized by chronic, unprovoked and recurrent seizures, which are the result of rapid and excessive bioelectric discharges in nerve cells. Neuroimaging is used to detect underlying structural abnormalities which may be associated with epilepsy. This paper reviews the most common abnormalities, such as hippocampal sclerosis, malformations of cortical development and vascular malformation, detected by neuroimaging in patients with epilepsy to help understand the correlation between these changes and the course, treatment and prognosis of epilepsy. Magnetic resonance imaging (MRI) reveals structural changes in the brain which are described in this review. Recent studies indicate the usefulness of additional imaging techniques. The use of fluorodeoxyglucose positron emission tomography (FDG-PET) improves surgical outcomes in MRI-negative cases of focal cortical dysplasia. Some techniques, such as quantitative image analysis, magnetic resonance spectroscopy (MRS), functional MRI (fMRI), diffusion tensor imaging (DTI) and fibre tract reconstruction, can detect small malformations—which means that some of the epilepsies can be treated surgically. Quantitative susceptibility mapping may become the method of choice in vascular malformations. Neuroimaging determines appropriate diagnosis and treatment and helps to predict prognosis.
Healing of Chronic Wounds by Copper Oxide-Impregnated Wound Dressings—Case Series
Authors: Melamed Eyal , Kiambi Patrick , Okoth Dancan , Honigber Irena , Tamir Eran , Borkow Gadi
Published: March 2021

Novel antimicrobial wound dressings impregnated with copper oxide micro-particles have been cleared for treatment of acute and chronic wounds. Our objective is to provide preliminary data regarding the potential benefit of using these novel wound dressings including in non-infected wounds. Methods involved the treatment of wounds that responded partially or poorly to conventional wound healing treatments with copper oxide impregnated wound dressings in patients with a range of etiologies. Ten cases of patients with etiologies such as diabetes mellitus, sickle cell disease, renal failure, and necrotizing fasciitis, in which the application of copper oxide impregnated wound dressings in infected and non-infected wounds, which resulted in significant enhanced wound healing, are presented. This was exemplified by clearing of the wound infections, reduction of the fibrous and/or necrotic tissue and by intense granulation, epithelialization, and wound closure. The described 10 case reports support our hypothesis that the copper oxide-containing wound dressing not only confers protection to the wound and the dressing from microbial contamination, and in some cases may help clear the wound infections, but in addition and more importantly, stimulate skin regeneration and wound healing. Our findings are in line with previous animal and in vitro studies showing that copper plays a key role in angiogenesis and skin regeneration. These case reports support the notion that the use of copper oxide impregnated wound dressings may be an important intervention in the arsenal of wound treatment modalities, especially in hard to heal wounds.
Use of Public Automated External Defibrillators in Out-of-Hospital Cardiac Arrest in Poland
Authors: Żuratyński Przemysław , Ślęzak Daniel , Dąbrowski Sebastian , Krzyżanowski Kamil , Mędrzycka-Dąbrowska Wioletta , Rutkowski Przemysław
Published: March 2021

Background and objectives: National medical records indicate that approximately 350,000–700,000 people die each year from sudden cardiac arrest. The guidelines of the European Resuscitation Council (ERC) and the International Liaison Committee on Resuscitation (ILCOR) indicate that in addition to resuscitation, it is important—in the case of so-called defibrillation rhythms—to perform defibrillation as quickly as possible. The aim of this study was to assess the use of public automated external defibrillators in out of hospital cardiac arrest in Poland between 2008 and 2018. Materials and Methods: One hundred and twenty cases of use of an automated external defibrillator placed in a public space between 2008 and 2018 were analyzed. The study material consisted of data on cases of use of an automated external defibrillator in adults (over 18 years of age). Only cases of automated external defibrillators (AED) use in a public place other than a medical facility were analysed, additionally excluding emergency services, i.e., the State Fire Service and the Volunteer Fire Service, which have an AED as part of their emergency equipment. The survey questionnaire was sent electronically to 1165 sites with AEDs and AED manufacturers. A total of 298 relevant feedback responses were received. Results: The analysis yielded data on 120 cases of AED use in a public place. Conclusions: Since 2016, there has been a noticeable increase in the frequency of use of AEDs located in public spaces. This is most likely related to the spread of public access to defibrillation and increased public awareness.
Elemental and Isotopic Characterization of Tobacco from Umbria
Authors: Bontempo Luana , Bertoldi Daniela , Franceschi Pietro , Rossi Fabio , Larcher Roberto
Published: March 2021

Umbrian tobacco of the Virginia Bright variety is one of the most appreciated tobaccos in Europe, and one characterized by an excellent yield. In recent years, the Umbria region and local producers have invested in introducing novel practices (for production and processing) focused on environmental, social, and economic sustainability. Due to this, tobacco from Umbria is a leading commodity in the global tobacco industry, and it claims a high economic value. The aim of this study is then to assess if elemental and isotopic compositions can be used to protect the quality and geographical traceability of this particular tobacco. For the first time the characteristic value ranges of the stable isotope ratios of the bio-elements as a whole (δ2H, δ13C, δ15N, δ18O, and δ34S) and of the concentration of 56 macro- and micro-elements are now available, determined in Virginia Bright tobacco produced in two different areas of Italy (Umbria and Veneto), and from other worldwide geographical regions. The ranges of variability of elements and stable isotope ratios had slightly different results, according to the three geographical origins considered. In particular, Umbria samples presented significantly lower content of metals potentially dangerous for human health. The results of this first exploratory work highlight the possibility of characterizing tobacco from Umbria, and suggest widening the scope of the survey throughout Italy and foreign regions, in order to be used to describe the geographical origin of tobacco in general and verify the origin of the products on the market.
In Silico Prediction and Analysis of Unusual Lantibiotic Resistance Operons in the Genus Corynebacterium
Authors: Goldbeck Oliver , Weixler Dominik , Eikmanns Bernhard J. , Riedel Christian U.
Published: March 2021

Post-translationally modified, (methyl-)lanthionine-containing peptides are produced by several Gram-positive bacteria. These so-called lantibiotics have potent activity against various bacterial pathogens including multidrug-resistant strains and are thus discussed as alternatives to antibiotics. Several naturally occurring mechanisms of resistance against lantibiotics have been described for bacteria, including cell envelope modifications, ABC-transporters, lipoproteins and peptidases. Corynebacterium species are widespread in nature and comprise important pathogens, commensals as well as environmentally and biotechnologically relevant species. Yet, little is known about lantibiotic biosynthesis and resistance in this genus. Here, we present a comprehensive in silico prediction of lantibiotic resistance traits in this important group of Gram-positive bacteria. Our analyses suggest that enzymes for cell envelope modification, peptidases as well as ABC-transporters involved in peptide resistance are widely distributed in the genus. Based on our predictions, we analyzed the susceptibility of six Corynebacterium species to nisin and found that those without dedicated resistance traits are more susceptible and unable to adapt to higher concentrations. In addition, we were able to identify lantibiotic resistance operons encoding for peptidases, ABC-transporters and two-component systems with an unusual predicted structure that are conserved in the genus Corynebacterium. Heterologous expression shows that these operons indeed confer resistance to the lantibiotic nisin.
Dynamics of Gut Microbiota Recovery after Antibiotic Exposure in Young and Old Mice (A Pilot Study)
Authors: Laubitz Daniel , Typpo Katri , Midura-Kiela Monica , Brown Clairessa , Barberán Albert , Ghishan Fayez K. , Kiela Pawel R.
Published: March 2021

Antibiotics have improved survival from previously deadly infectious diseases. Antibiotics alter the microbial composition of the gut microbiota, and these changes are associated with diminished innate immunity and decline in cognitive function in older adults. The composition of the human microbiota changes with age over the human lifespan. In this pilot study, we sought to identify if age is associated with differential recovery of the microbiota after antibiotic exposure. Using 16S rRNA gene sequencing, we compared recovery of the gut microbiota after the 10-day broad-spectrum antibiotic treatment in wild-type C57BL/six young and older mice. Immediately after antibiotic cessation, as expected, the number of ASVs, representing taxonomic richness, in both young and older mice significantly declined from the baseline. Mice were followed up to 6 months after cessation of the single 10-day antibiotic regimen. The Bray-Curtis index recovered within 20 days after antibiotic cessation in young mice, whereas in older mice the microbiota did not fully recover during the 6-months of follow-up. Bifidobacterium, Dubosiella, Lachnospiraceae_NK4A136_group became dominant in older mice, whereas in young mice, the bacteria were more evenly distributed, with only one dominant genus of Anaeroplasma. From 45 genera that became extinct after antibiotic treatment in young mice, 31 (68.9%) did not recover by the end of the study. In older mice, from 36 extinct genera, 27 (75%) did not recover. The majority of the genera that became extinct and never recovered belonged to Firmicutes phylum and Clostridiales family. In our study, age was a factor associated with the long-term recovery of the gut microbiota after the 10-day antibiotic treatment.
In-Situ Metatranscriptomic Analyses Reveal the Metabolic Flexibility of the Thermophilic Anoxygenic Photosynthetic Bacterium Chloroflexus aggregans in a Hot Spring Cyanobacteria-Dominated Microbial Mat
Authors: Kawai Shigeru , Martinez Joval N. , Lichtenberg Mads , Trampe Erik , Kühl Michael , Tank Marcus , Haruta Shin , Nishihara Arisa , Hanada Satoshi , Thiel Vera
Published: March 2021

Chloroflexus aggregans is a metabolically versatile, thermophilic, anoxygenic phototrophic member of the phylum Chloroflexota (formerly Chloroflexi), which can grow photoheterotrophically, photoautotrophically, chemoheterotrophically, and chemoautotrophically. In hot spring-associated microbial mats, C. aggregans co-exists with oxygenic cyanobacteria under dynamic micro-environmental conditions. To elucidate the predominant growth modes of C. aggregans, relative transcription levels of energy metabolism- and CO2 fixation-related genes were studied in Nakabusa Hot Springs microbial mats over a diel cycle and correlated with microscale in situ measurements of O2 and light. Metatranscriptomic analyses indicated two periods with different modes of energy metabolism of C. aggregans: (1) phototrophy around midday and (2) chemotrophy in the early morning hours. During midday, C. aggregans mainly employed photoheterotrophy when the microbial mats were hyperoxic (400–800 µmol L−1 O2). In the early morning hours, relative transcription peaks of genes encoding uptake hydrogenase, key enzymes for carbon fixation, respiratory complexes as well as enzymes for TCA cycle and acetate uptake suggest an aerobic chemomixotrophic lifestyle. This is the first in situ study of the versatile energy metabolism of C. aggregans based on gene transcription patterns. The results provide novel insights into the metabolic flexibility of these filamentous anoxygenic phototrophs that thrive under dynamic environmental conditions.
Comparison of Coated and Immobilized Chiral Stationary Phases Based on Amylose tris-[(S)-α-Methylbenzylcarbamate] for the HPLC Enantiomer Separation of α-Lipoic Acid and Its Reduced Form
Authors: Rosetti Alessia , Villani Claudio , Pierini Marco , Cirilli Roberto
Published: March 2021

The couple of chiral sulfur compounds α-lipoic acid (ALA)/α-dihydrolipoic acid (DHALA) has attracted considerable attention in recent years owing to its remarkable anti-inflammatory and antioxidant properties. It is well known that the chirality of the C6 plays a key role in determining the biological activity of ALA. The natural occurring (R)-ALA enantiomer is an essential cofactor for key oxidative metabolism enzyme complexes and, after oral administration of the racemic mixture, it shows higher plasma concentration than (S)-ALA. Differently, the in vivo enantioselective action difference between the enantiomers of DHALA has not yet been studied. This lacking is perhaps due to the unavailability of analytical methods capable of determining the enantiomeric composition of biological samples during pharmacokinetic and pharmacodynamic events. In the present work, the direct and baseline enantioresolution of both chiral acids by HPLC on two amylose-derived chiral stationary phases is presented. The proposed chiral enantioselective protocol, therefore, does not require pre- or on-column derivatization. The performance of the coated Chiralpak AS-H CSP and the new immobilized Chiralpak IH-3 CSP, which have the same chiral selector amylose tris-[(S)-α-methylbenzylcarbamate], were compared using conventional normal-phase mobile phases containing ethanol or 2-propanol as alcoholic solvents and a fixed percentage of trifluoroacetic acid. Nonconventional eluents containing dichloromethane, ethyl acetate, and 2-methyltetrahydrofuran as organic cosolvents were applied in the separation of the enantiomers of two carboxylic acids on the immobilized Chiralpak IH-3 CSP. The effect of the column temperature was carefully evaluated in order to improve enantioselectivity. Adequate amounts of enantiomers were isolated by an analytical-size Chiralpak IH-3 column and submitted to chiroptical measurements. The absolute configuration assignment of the isolated enantiomers was determined by a multidisciplinary procedure based on the comparison of the experimental and calculated chiroptical properties.
3-Carboxylic Acid and Formyl-Derived Coumarins as Photoinitiators in Photo-Oxidation or Photo-Reduction Processes for Photopolymerization upon Visible Light: Photocomposite Synthesis and 3D Printing Applications
Authors: Rahal Mahmoud , Graff Bernadette , Toufaily Joumana , Hamieh Tayssir , Noirbent Guillaume , Gigmes Didier , Dumur Frédéric , Lalevée Jacques
Published: March 2021

In this paper, nine organic compounds based on the coumarin scaffold and different substituents were synthesized and used as high-performance photoinitiators for free radical photopolymerization (FRP) of meth(acrylate) functions under visible light irradiation using LED at 405 nm. In fact, these compounds showed a very high initiation capacity and very good polymerization profiles (both high rate of polymerization (Rp) and final conversion (FC)) using two and three-component photoinitiating systems based on coum/iodonium salt (0.1%/1% w/w) and coum/iodonium salt/amine (0.1%/1%/1% w/w/w), respectively. To demonstrate the efficiency of the initiation of photopolymerization, several techniques were used to study the photophysical and photochemical properties of coumarins, such as: UV-visible absorption spectroscopy, steady-state photolysis, real-time FTIR, and cyclic voltammetry. On the other hand, these compounds were also tested in direct laser write experiments (3D printing). The synthesis of photocomposites based on glass fiber or carbon fiber using an LED conveyor at 385 nm (0.7 W/cm2) was also examined.
Polymeric Nanovectors Incorporated with Ganciclovir and HSV-tk Encoding Plasmid for Gene-Directed Enzyme Prodrug Therapy
Authors: Sawdon Alicia J. , Zhang Jun , Peng Sarah , Alyami Esmael M. , Peng Ching-An
Published: March 2021

In the area of gene-directed enzyme prodrug therapy (GDEPT), using herpes simplex virus thymidine kinase (HSV-tk) paired with prodrug ganciclovir (GCV) for cancer treatment has been extensively studied. It is a process involved with two steps whereby the gene (HSV-tk) is first delivered to malignant cells. Afterward, non-toxic GCV is administered to that site and activated to cytotoxic ganciclovir triphosphate by HSV-tk enzyme expressed exogenously. In this study, we presented a one-step approach that both gene and prodrug were delivered at the same time by incorporating them with polymeric micellar nanovectors. GCV was employed as an initiator in the ring-opening polymerization of ε-caprolactone (ε-CL) to synthesize hydrophobic GCV-poly(caprolactone) (GCV–PCL), which was furthered grafted with hydrophilic chitosan to obtain amphiphilic polymer (GCV–PCL–chitosan) for the fabrication of self-assembled micellar nanoparticles. The synthesized amphiphilic polymer was characterized using Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. Micellar prodrug nanoparticles were analyzed by dynamic light scattering, zeta potential, critical micelle concentration, and transmission electron microscopy. Polymeric prodrug micelles with optimal features incorporated with HSV-tk encoding plasmids were cultivated with HT29 colorectal cancer cells and anticancer effectiveness was determined. Our results showed that prodrug GCV and HSV-tk cDNA encoded plasmid incorporated in GCV–PCL–chitosan polymeric nanocarriers could be delivered in a one-step manner to HT-29 cells and triggered high cytotoxicity.
Cannabinoid Quinones—A Review and Novel Observations
Authors: Kogan Natalya M. , Peters Maximilian , Mechoulam Raphael
Published: March 2021

A cannabinoid anticancer para-quinone, HU-331, which was synthesized by our group five decades ago, was shown to have very high efficacy against human cancer cell lines in-vitro and against in-vivo grafts of human tumors in nude mice. The main mechanism was topoisomerase IIα catalytic inhibition. Later, several groups synthesized related compounds. In the present presentation, we review the publications on compounds synthesized on the basis of HU-331, summarize their published activities and mechanisms of action and report the synthesis and action of novel quinones, thus expanding the structure-activity relationship in these series.
Computational Modeling to Explain Why 5,5-Diarylpentadienamides are TRPV1 Antagonists
Authors: Caballero Julio
Published: March 2021

Several years ago, the crystallographic structures of the transient receptor potential vanilloid 1 (TRPV1) in the presence of agonists and antagonists were reported, providing structural information about its chemical activation and inactivation. TRPV1’s activation increases the transport of calcium and sodium ions, leading to the excitation of sensory neurons and the perception of pain. On the other hand, its antagonistic inactivation has been explored to design analgesic drugs. The interactions between the antagonists 5,5-diarylpentadienamides (DPDAs) and TRPV1 were studied here to explain why they inactivate TRPV1. The present work identified the structural features of TRPV1–DPDA complexes, starting with a consideration of the orientations of the ligands inside the TRPV1 binding site by using molecular docking. After this, a chemometrics analysis was performed (i) to compare the orientations of the antagonists (by using LigRMSD), (ii) to describe the recurrent interactions between the protein residues and ligand groups in the complexes (by using interaction fingerprints), and (iii) to describe the relationship between topological features of the ligands and their differential antagonistic activities (by using a quantitative structure–activity relationship (QSAR) with 2D autocorrelation descriptors). The interactions between the DPDA groups and the residues Y511, S512, T550, R557, and E570 (with a recognized role in the binding of classic ligands), and the occupancy of isoquinoline or 3-hydroxy-3,4-dihydroquinolin-2(1H)-one groups of the DPDAs in the vanilloid pocket of TRPV1 were clearly described. Based on the results, the structural features that explain why DPDAs inactivate TRPV1 were clearly exposed. These features can be considered for the design of novel TRPV1 antagonists.
Inhibitory Effect of LGS and ODE Isolated from the Twigs of Syringa oblata subsp. dilatata on RANKL-Induced Osteoclastogenesis in Macrophage Cells
Authors: Kim Ga-Ram , Kim Eun-Nam , Park Kyoung Jin , Kim Ki Hyun , Jeong Gil-Saeng
Published: March 2021

Osteoblasts and osteoclasts play a pivotal role in maintaining bone homeostasis, of which excessive bone resorption by osteoclasts can cause osteoporosis and various bone diseases. However, current osteoporosis treatments have many side effects, and research on new treatments that can replace these treatments is ongoing. Therefore, in this study, the roles of ligustroside (LGS) and oleoside dimethylester (ODE), a natural product-derived compound isolated from Syringa oblata subsp. dilatata as a novel, natural product-derived osteoporosis treatments were investigated. In the results of this study, LGS and ODE inhibited the differentiation of receptor activator of nuclear factor kappa-Β ligand (RANKL)-induced RAW264.7 cells into osteoclasts without cytotoxicity, and down-regulated the activity of TRAP, a specific biomarker of osteoclasts. In addition, it inhibited bone resorption and actin ring formation, which are important functions and features of osteoclasts. Also, the effects of LGS and ODE on the mitogen-activated protein kinase (MAPK) and nuclear factor kappa-light-chain-enhancer of activated B (NF-κB) and phosphoinositide 3-kinases (PI3K)/ protein kinase B (Akt)/mechanistic target of rapamycin (mTOR) signaling pathways that play important roles in osteoclast differentiation were evaluated. In the results, LGS and ODE downregulated the phosphorylation of RANKL-induced MAPK and PI3K/Akt/mTOR proteins in a concentration-dependent manner, translocation of NF-κB into the nucleus was inhibited. As a result, the compounds LGS and ODE isolated from S. oblate subsp. dilatata effectively regulated the differentiation of RANKL-induced osteoclasts and inhibited the phosphorylation of signaling pathways that play a pivotal role in osteoclast differentiation. Therefore, these results suggest the possibility of LGS and ODE as new natural product treatments for bone diseases caused by excessive osteoclasts.
The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues
Authors: Schlachter Adrien , Fleury Alexandre , Tanner Kevin , Soldera Armand , Habermeyer Benoit , Guilard Roger , Harvey Pierre D.
Published: March 2021

The derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) are pivotal ingredients for a large number of functional, stimuli-responsive materials and therapeutic molecules based on their photophysical properties, and there is a urgent need to understand and predict their optical traits prior to investing a large amount of resources in preparing them. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations were performed to calculate the excitation energies of the lowest-energy singlet excited state of a large series of common BODIPY derivatives employing various functional aiming at the best possible combination providing the least deviations from the experimental values. Using the common “fudge” correction, a series of combinations was investigated, and a methodology is proposed offering equal or better performances than what is reported in the literature.
One-Step Preparation of Chitosan-Based Magnetic Adsorbent and Its Application to the Adsorption of Inorganic Arsenic in Water
Authors: Jiang Zhe , Li Nian , Li Pei-Ying , Liu Bo , Lai Hua-Jie , Jin Tao
Published: March 2021

Chitosan is a kind of biodegradable natural polysaccharide, and it is a very promising adsorber material for removing metal ions from aqueous solutions. In this study, chitosan-based magnetic adsorbent CMC@Fe3O4 was synthesized by a one-step method using carboxymethyl chitosan (CMC) and ferric salts under relatively mild conditions. The Fe3O4 microspheres were formed and the core–shell structure of CMC@Fe3O4 was synthesized in the meantime, which was well characterized via SEM/TEM, XRD, VSM, FT-IR, thermo gravimetric analysis (TGA), XPS, size distribution, and zeta potential. The effects of initial arsenic concentration, pH, temperature, contact time, and ionic strength on adsorption quantity of inorganic arsenic was studied through batch adsorption experiments. The magnetic adsorbent CMC@Fe3O4 displayed satisfactory adsorption performance for arsenic in water samples, up to 20.1 mg/g. The optimal conditions of the adsorption process were pH 3.0, 30−50 °C, and a reaction time of 15 min. The adsorption process can be well described by pseudo-second-order kinetic model, suggesting that chemisorption was main rate-controlling step. The Langmuir adsorption model provided much higher correlation coefficient than that of Freundlich adsorption model, indicating that the adsorption behavior is monolayer adsorption on the surface of the magnetic adsorbents. The above results have demonstrated that chitosan-based magnetic adsorbent CMC@Fe3O4 is suitable for the removal of inorganic arsenic in water.
Improved Diazo-Transfer Reaction for DNA-Encoded Chemistry and Its Potential Application for Macrocyclic DEL-Libraries
Authors: Ede Selahattin , Schenk Mandy , Bierer Donald , Weinmann Hilmar , Graham Keith
Published: March 2021

DNA-encoded libraries (DEL) are increasingly being used to identify new starting points for medicinal chemistry in drug discovery. Herein, we discuss the development of methods that allow the conversion of both primary amines and anilines, attached to DNA, to their corresponding azides in excellent yields. The scope of these diazo-transfer reactions was investigated, and a proof-of-concept has been devised to allow for the synthesis of macrocycles on DNA.
Building an Emotionally Responsive Avatar with Dynamic Facial Expressions in Human—Computer Interactions
Authors: Wang Heting , Gaddy Vidya , Beveridge James Ross , Ortega Francisco R.
Published: March 2021

The role of affect has been long studied in human–computer interactions. Unlike previous studies that focused on seven basic emotions, an avatar named Diana was introduced who expresses a higher level of emotional intelligence. To adapt to the users various affects during interaction, Diana simulates emotions with dynamic facial expressions. When two people collaborated to build blocks, their affects were recognized and labeled using the Affdex SDK and a descriptive analysis was provided. When participants turned to collaborate with Diana, their subjective responses were collected and the length of completion was recorded. Three modes of Diana were involved: a flat-faced Diana, a Diana that used mimicry facial expressions, and a Diana that used emotionally responsive facial expressions. Twenty-one responses were collected through a five-point Likert scale questionnaire and the NASA TLX. Results from questionnaires were not statistically different. However, the emotionally responsive Diana obtained more positive responses, and people spent the longest time with the mimicry Diana. In post-study comments, most participants perceived facial expressions on Diana’s face as natural, four mentioned uncomfortable feelings caused by the Uncanny Valley effect.