bluuebunny/crossref_metadata_2025 huggingface dataset:
State-of-the-Art Ceramic Membranes for Oily Wastewater Treatment: Modification and Application
Authors: Chen Mingliang , Heijman Sebastiaan G. J. , Rietveld Luuk C.
Published: November 2021

Membrane filtration is considered to be one of the most promising methods for oily wastewater treatment. Because of their hydrophilic surface, ceramic membranes show less fouling compared with their polymeric counterparts. Membrane fouling, however, is an inevitable phenomenon in the filtration process, leading to higher energy consumption and a shorter lifetime of the membrane. It is therefore important to improve the fouling resistance of the ceramic membranes in oily wastewater treatment. In this review, we first focus on the various methods used for ceramic membrane modification, aiming for application in oily wastewater. Then, the performance of the modified ceramic membranes is discussed and compared. We found that, besides the traditional sol-gel and dip-coating methods, atomic layer deposition is promising for ceramic membrane modification in terms of the control of layer thickness, and pore size tuning. Enhanced surface hydrophilicity and surface charge are two of the most used strategies to improve the performance of ceramic membranes for oily wastewater treatment. Nano-sized metal oxides such as TiO2, ZrO2 and Fe2O3 and graphene oxide are considered to be the potential candidates for ceramic membrane modification for flux enhancement and fouling alleviation. The passive antifouling ceramic membranes, e.g., photocatalytic and electrified ceramic membranes, have shown some potential in fouling control, oil rejection and flux enhancement, but have their limitations.
Nanodrug Transmembrane Transport Research Based on Fluorescence Correlation Spectroscopy
Authors: Gao Xinwei , Liu Yanfeng , Zhang Jia , Wang Luwei , Guo Yong , Zhu Yinru , Yang Zhigang , Yan Wei , Qu Junle
Published: November 2021

Although conventional fluorescence intensity imaging can be used to qualitatively study the drug toxicity of nanodrug carrier systems at the single-cell level, it has limitations for studying nanodrug transport across membranes. Fluorescence correlation spectroscopy (FCS) can provide quantitative information on nanodrug concentration and diffusion in a small area of the cell membrane; thus, it is an ideal tool for studying drug transport across the membrane. In this paper, the FCS method was used to measure the diffusion coefficients and concentrations of carbon dots (CDs), doxorubicin (DOX) and CDs-DOX composites in living cells (COS7 and U2OS) for the first time. The drug concentration and diffusion coefficient in living cells determined by FCS measurements indicated that the CDs-DOX composite distinctively improved the transmembrane efficiency and rate of drug molecules, in accordance with the conclusions drawn from the fluorescence imaging results. Furthermore, the effects of pH values and ATP concentrations on drug transport across the membrane were also studied. Compared with free DOX under acidic conditions, the CDs-DOX complex has higher cellular uptake and better transmembrane efficacy in U2OS cells. Additionally, high concentrations of ATP will cause negative changes in cell membrane permeability, which will hinder the transmembrane transport of CDs and DOX and delay the rapid diffusion of CDs-DOX. The results of this study show that the FCS method can be utilized as a powerful tool for studying the expansion and transport of nanodrugs in living cells, and might provide a new drug exploitation strategy for cancer treatment in vivo.
Defectoscopic and Geometric Features of Defects That Occur in Sheet Metal and Their Description Based on Statistical Analysis
Authors: Konovalenko Ihor , Maruschak Pavlo , Kozbur Halyna , Brezinová Janette , Brezina Jakub , Guzanová Anna
Published: November 2021

Features of the defect class “scratches, attritions, lines”, their geometric structure, and their causes are analyzed. An approach is developed that defines subclasses within this class of technological defects based on additional analysis of morphological features. The analysis of the reasons for these subclasses allows additional information to be obtained about the rolling process, identifying additional signs of defects, regulating the rolling conditions of steel strips more accurately, and diagnosing the equipment condition.
Investigation of Slow Eutectoid Element on Tensile Properties and Superplasticity of a Forged SP700 Titanium Alloy
Authors: Han Dong , Zhao Yongqing , Zeng Weidong , Xiang Junfeng
Published: November 2021

The tensile properties and superplasticity of a forged SP700 alloy with slow eutectoid element (1.5%Cr) addition were investigated in the present paper. The results of the microstructures showed that slow eutectoid element Cr has a significant influence on stabilizing the β phase and the SP700Cr alloy showed a uniform duplex and completely globular microstructure after annealing at 820 °C for 1 h and aging at 500 °C for 6 h. The results of the tensile tests showed that the yield strength, ultimate tensile strength and elongation of the alloy with optimized microstructure were 1312 MPa, 1211 MPa and 10% at room temperature, and the elongation was achieved to 1127% at 770 °C. Compared with that of the SP700 alloy, the strain rate sensitivity of the SP700Cr alloy showed a higher value. The microstructures after elevated temperature tensile tests showed that the higher density of dislocations and twins exists in SP700 alloy and the lower density of dislocations favor distribution in SP700Cr alloy. Based on the above results, the tensile properties and superplasticity of the forged SP700 alloy with 1.5% Cr addition was analyzed. In addition, microstructure characteristics were investigated by the TEM and EBSD technologies.
Effect of the Hot Deformation Conditions on Structure and Mechanical Properties of AlCr/AlCrSi Powder Composites
Authors: Korosteleva Elena N. , Pribytkov Gennady A. , Korzhova Victoria V.
Published: November 2021

Aluminum matrix composites usually contain strengthening particles of refractory compounds (SiC, Al2O3) that do not react with the Al matrix. There is a problem in producing the Al matrix composite with inclusion of metals that can generate intermetallic compounds with aluminum. In this case, a conventional sintering of powder mixtures results in high porosity due to volume growth. That is why some new methods of producing dense Al matrix composites are required. A possibility to create a dense powder Al-based composite containing hard components, such as chromium and silicon, without using the sintering process, is considered. This paper presents study results of structural and mechanical properties of Al-Cr and Al-Cr-Si composites produced by hot compaction of powder mixtures. An analysis of the relationship between mechanical properties and structures of Al-Cr and Al-Cr-Si composites is carried out. Optimal values for thermomechanical processing modes that ensure sufficient strength and plasticity are determined. It is shown that strong bonding of the aluminum particles occurs under hot deformation, and an aluminum matrix is formed that provides acceptable composite bending strength as a result. The presence of chromium and silicon hard inclusions is not a significant obstacle for aluminum plastic flow. Al-Cr and Al-Cr-Si composites produced by hot deformation of the powder mixtures can be used as cathode material for the deposition of wear-resistant nitride coatings on metalworking tools.
Microstructural Evolution and Electrochemical Behavior of Solution Treated, Hot Rolled and Aged MgDyZnZr Alloy
Authors: de Freitas Bruno Xavier , Antonini Leonardo A. , Cury Paula L. C. T. , da Silva Viviane L. F. , Chaia Nabil , Tomachuk Célia R. , Mathieu Stéphane , Coelho Gilberto C. , dos Santos Claudinei , Nunes Carlos A.
Published: November 2021

In order to develop a potential route to fabricate plates and clips for orthopedic applications, a Mg–3.4Dy–0.2Zn–0.4Zr (wt.%) alloy was produced and analyzed in different conditions: solution treated at 525 °C for 3 h, hot rolled and hot rolled and aged at 250 °C. The aging behavior of the rolled alloy was investigated during isothermal aging at 250 °C, and a significant peak was observed at 10 h. The electrochemical behavior was evaluated in 0.9 wt.% NaCl solution at 37 ± 0.5 °C by potentiodynamic polarization and electrochemical impedance spectroscopy. The 525 °C-3 h and hot rolled specimens exhibited corrosion rates of 2.0 and 1.7 mm/year, respectively. The hot rolled and aged at 250 °C for 10 h specimen presented a grain size of 11.8 ± 1.7 μm with an intense macrotexture of the basal {0002} plane, hardness of 73 ± 3 HV and higher impedance modulus and obtained the highest corrosion resistance with a corrosion rate of 0.9 mm/year.
Masking Effect of LPSO Structure Phase on Wear Transition in Mg97Zn1Y2 Alloy
Authors: Tao Fujun , Duan Hongfei , Zhao Lijun , An Jian
Published: November 2021

Room- and elevated-temperature wear tests were conducted using a pin-on-disk testing machine to study wear behavior of Mg97Zn1Y2 alloy and role of long-period-stacking-ordered (LPSO) structure phase in mild–severe wear transition (SWT). Variation of wear rate exhibited a three-stage characteristic with load at various test temperatures, i.e., a gradual increasing stage, a slightly higher plateau stage, and a rapid rising stage. The wear mechanisms in the three stages were identified using scanning electron microscope (SEM), from which the first stage was confirmed as mild wear, and the other two stages were verified as severe wear. The interdendritic LPSO structure phase was elongated into strips along the sliding direction with Mg matrix deformation in the subsurface, plate-like LPSO structure phase precipitated at elevated temperatures of 150 and 200 °C. The fiber enhancement effect and precipitation effect of LPSO structure phase resulted in a little difference in wear rate between the first and second stages, i.e., a masking effect on SWT. Microstructure and microhardness were examined in the subsurfaces, from which the mechanism for SWT was confirmed to be dynamic recrystallization (DRX) softening. There is an apparently linear correlation between the critical load for SWT and test temperature, indicating that SWT is governed by a common critical DRX temperature.
Thermographic Analysis of Composite Metallization through Cold Spray
Authors: Heydari Astaraee Asghar , Salerno Antonio , Bagherifard Sara , Carlone Pierpaolo , Parmar Hetal , Astarita Antonello , Viscusi Antonio , Colombo Chiara
Published: November 2021

Cold Spray is an innovative technology to create coatings through the impact of metallic particles on substrates. Its application to composites’ surfaces is recently attracting the attention of the scientific community thanks to the possibility to functionalize and improve their thermal and wear properties. Within this context, the generation of the first metal-to-composite layer is fundamental. This work presented an experimental investigation of a composite panel, reinforced with glass fibers and coated with aluminum particles. The coating investigation was carried out through active pulsed thermography, analyzing the thermal response of single and double hatches. The thermal outputs were compared with a standard microscopic analysis, with a critical discussion supporting the identification of factors that influence the thermal response to the pulse: (1) layer’s thickness; (2) cold spray coverage; (3) layer compactness; (4) particle-substrate adhesion; (5) particle’s oxidation; and (6) surface roughness.
Corrosion Inhibition Properties of Thiazolidinedione Derivatives for Copper in 3.5 wt.% NaCl Medium
Authors: Lgaz Hassane , Saha Sourav Kr. , Lee Han-seung , Kang Namhyun , Thari Fatima Zahra , Karrouchi Khalid , Salghi Rachid , Bougrin Khalid , Ali Ismat Hassan
Published: November 2021

Copper is the third-most-produced metal globally due to its exceptional mechanical and thermal properties, among others. However, it suffers serious dissolution issues when exposed to corrosive mediums. Herein, two thiazolidinedione derivatives, namely, (Z)-5-(4-methylbenzylidene)thiazolidine-2,4-dione (MTZD) and (Z)-3-allyl-5-(4-methylbenzylidene)thiazolidine-2,4-dione (ATZD), were synthesized and applied for corrosion protection of copper in 3.5 wt.% NaCl medium. The corrosion inhibition performance of tested compounds was evaluated at different experimental conditions using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves (PPC) and atomic force microscopy (AFM). EIS results revealed that the addition of studied inhibitors limited the dissolution of copper in NaCl solution, leading to a high polarization resistance compared with the blank solution. In addition, PPC suggested that tested compounds had a mixed-type effect, decreasing anodic and cathodic corrosion reactions. Moreover, surface characterization by AFM indicated a significant decrease in surface roughness of copper after the addition of inhibitors. Outcomes from the present study suggest that ATZD (IE% = 96%) outperforms MTZD (IE% = 90%) slightly, due to the presence of additional –C3H5 unit (–CH2–CH = CH2) in the molecular scaffold of MTZD.
The Echocardiographic Parameters of Systolic Function Are Associated with Specific Metabolomic Fingerprints in Obstructive and Non-Obstructive Hypertrophic Cardiomyopathy
Authors: Deidda Martino , Noto Antonio , Pasqualucci Daniele , Fattuoni Claudia , Barberini Luigi , Piras Cristina , Bassareo Pier Paolo , Porcu Maurizio , Mercuro Giuseppe , Dessalvi Christian Cadeddu
Published: November 2021

The purpose of this study was to assess whether metabolomics, associated with echocardiography, was able to highlight pathophysiological differences between obstructive (OHCM) or non-obstructive (NOHCM) hypertrophic cardiomyopathy. Thirty-one HCM patients underwent standard and advanced echocardiography; a plasma sample was collected for metabolomic analysis. Results. Patients with OHCM compared with subjects with NOHCM had higher values of 2DLVEF (66.5 ± 3.3% vs. 60.6 ± 1.8%, p < 0.01), S wave (7.6 ± 1.1 vs. 6.3 ± 0.7 cm/s, p < 0.01) and 3D global longitudinal strain (17.2 ± 4.2%, vs. 13.4 ± 1.3%, p < 0.05). A 2-group PLS-Discriminant Analysis was performed to verify whether the two HCM groups differed also based on the metabolic fingerprint. A clear clustering was shown (ANOVA p = 0.014). The most discriminating metabolites resulted as follows: in the NOHCM Group, there were higher levels of threitol, aminomalonic acid, and sucrose, while the OHCM Group presented higher levels of amino acids, in particular those branched chains, of intermediates of glycolysis (lactate) and the Krebs cycle (fumarate, succinate, citrate), of fatty acids (arachidonic acid, palmitoleic acid), of ketone bodies (2-OH-butyrate). Our data point out a different systolic function related to a specific metabolic activity in the two HCM phenotypic forms, with specific metabolites associated with better contractility in OHCM.
High-Throughput Analysis from Complex Matrices: Acoustic Ejection Mass Spectrometry from Phase-Separated Fluid Samples
Authors: Guo Yuzhu , Forbush Michael , Covey Thomas R. , Ghislain Lucien , Liu Chang
Published: November 2021

Acoustic ejection mass spectrometry is a novel high-throughput analytical technology that delivers high reproducibility without carryover observed. It eliminates the chromatography step used to separate analytes from matrix components. Fully-automated liquid–liquid extraction is widely used for sample cleanup, especially in high-throughput applications. We introduce a workflow for direct AEMS analysis from phase-separated liquid samples and explore high-throughput analysis from complex matrices. We demonstrate the quantitative determination of fentanyl from urine using this two-phase AEMS approach, with a LOD lower than 1 ng/mL, quantitation precision of 15%, and accuracy better than ±10% over the range of evaluation (1–100 ng/mL). This workflow offers simplified sample preparation and higher analytical throughput for some bioanalytical applications, in comparison to an LC-MS based approach.
Characterization of Giant Magnetostrictive Materials Using Three Complex Material Parameters by Particle Swarm Optimization
Authors: Chen Yukai , Yang Xin , Yang Mingzhi , Wei Yanfei , Zheng Haobin
Published: November 2021

Complex material parameters that can represent the losses of giant magnetostrictive materials (GMMs) are the key parameters for high-power transducer design and performance analysis. Since the GMMs work under pre-stress conditions and their performance is highly sensitive to pre-stress, the complex parameters of a GMM are preferably characterized in a specific pre-stress condition. In this study, an optimized characterization method for GMMs is proposed using three complex material parameters. Firstly, a lumped parameter model is improved for a longitudinal transducer by incorporating three material losses. Then, the structural damping and contact damping are experimentally measured and applied to confine the parametric variance ranges. Using the improved lumped parameter model, the real parts of the three key material parameters are characterized by fitting the experimental impedance data while the imaginary parts are separately extracted by the phase data. The global sensitivity analysis that accounts for the interaction effects of the multiple parameter variances shows that the proposed method outperforms the classical method as the sensitivities of all the six key parameters to both impedance and phase fitness functions are all high, which implies that the extracted material complex parameters are credible. In addition, the stability and credibility of the proposed parameter characterization is further corroborated by the results of ten random characterizations.
Universal Enzyme-Based Field Workflow for Rapid and Sensitive Quantification of Water Pathogens
Authors: Sun Angela , Stanton Jo-Ann L. , Bergquist Peter L. , Sunna Anwar
Published: November 2021

A universal filtration and enzyme-based workflow has been established to allow for the rapid and sensitive quantification of leading pathogens Cryptosporidium parvum, Giardia gamblia, Campylobacter jejuni, and Escherichia coli from tap water samples with volumes up to 100 mL, and the potential to scale up to larger volumes. qPCR limits of quantification as low as four oocysts for Cryptosporidium, twelve cysts for Giardia, two cells for C. jejuni, and nineteen cells for E. coli per reaction were achieved. A polycarbonate filter-based sampling method coupled with the prepGEM enzyme-based DNA extraction system created a single-step transfer workflow that required as little as 20 min of incubation time and a 100 µL reaction mix. The quantification via qPCR was performed directly on the prepGEM extract, bypassing time-consuming, labour-intensive conventional culture-based methods. The tap water samples were shown to contain insoluble particles that inhibited detection by reducing the quantification efficiency of a representative pathogen (C. jejuni) to 30–60%. This sample inhibition was effectively removed by an on-filter treatment of 20% (v/v) phosphoric acid wash. Overall, the established workflow was able to achieve quantification efficiencies of 92% and higher for all four leading water pathogens, forming the basis of a rapid, portable, and low-cost solution to water monitoring.
Role of the Sortase A in the Release of Cell-Wall Proteinase PrtS in the Growth Medium of Streptococcus thermophilus 4F44
Authors: Awussi Ahoefa Ablavi , Roux Emeline , Humeau Catherine , Hafeez Zeeshan , Maigret Bernard , Chang Oun Ki , Lecomte Xavier , Humbert Gérard , Miclo Laurent , Genay Magali , Perrin Clarisse , Dary-Mourot Annie
Published: November 2021

Growth of the lactic acid bacterium Streptococcus thermophilus in milk depends on its capacity to hydrolyze proteins of this medium through its surface proteolytic activity. Thus, strains exhibiting the cell envelope proteinase (CEP) PrtS are able to grow in milk at high cellular density. Due to its LPNTG motif, which is possibly the substrate of the sortase A (SrtA), PrtS is anchored to the cell wall in most S. thermophilus strains. Conversely, a soluble extracellular PrtS activity has been reported in the strain 4F44. It corresponds, in fact, to a certain proportion of PrtS that is not anchored to the cell wall but rather is released in the growth medium. The main difference between PrtS of strain 4F44 (PrtS4F44) and other PrtS concerns the absence of a 32-residue imperfect duplication in the prodomain of the CEP, postulated as being required for the maturation and correct subsequent anchoring of PrtS. In fact, both mature (without the prodomain at the N-terminal extremity) and immature (with the prodomain) forms are found in the soluble PrtS4F44 form along with an intact LPNTG at their C-terminal extremity. Investigations we present in this work show that (i) the imperfect duplication is not implied in PrtS maturation; (ii) the maturase PrtM is irrelevant in PrtS maturation which is probably automaturated; and (iii) SrtA allows for the PrtS anchoring in S. thermophilus but the SrtA of strain 4F44 (SrtA4F44) displays an altered activity.
Informed Local Smoothing in 3D Implicit Geological Modeling
Authors: von Harten Jan , de la Varga Miguel , Hillier Michael , Wellmann Florian
Published: November 2021

Geological models are commonly used to represent geological structures in 3D space. A wide range of methods exists to create these models, with much scientific work focusing recently on implicit representation methods, which perform an interpolation of a three-dimensional field where the relevant boundaries are then isosurfaces in this field. However, this method has well-known problems with inhomogeneous data distributions: if regions with densely sampled data points exist, modeling artifacts are common. We present here an approach to overcome this deficiency through a combination of an implicit interpolation algorithm with a local smoothing approach. The approach is based on the concepts of nugget effect and filtered kriging known from conventional geostatistics. It reduces the impact of regularly occurring modeling artifacts that result from data uncertainty and data configuration and additionally aims to improve model robustness for scale-dependent fit-for-purpose modeling. Local smoothing can either be manually adjusted, inferred from quantified uncertainties associated with input data or derived automatically from data configuration. The application for different datasets with varying configuration and noise is presented for a low complexity geologic model. The results show that the approach enables a reduction of artifacts, but may require a careful choice of parameter settings for very inhomogeneous data sets.
Guidelines to Study the Adsorption of Pesticides onto Clay Minerals Aiming at a Straightforward Evaluation of Their Removal Performance
Authors: Masini Jorge Cesar , Abate Gilberto
Published: November 2021

Natural and modified clay minerals have been extensively used for the adsorption/desorption of organic substances, especially pesticides, from waters and wastewater, aiming at pollution control and more efficient use of the herbicides through controlled release. While natural clay minerals efficiently remove organic cations such as paraquat and diquat, the adsorption of anionic or neutral species demands surface chemical modification with, for instance, quaternary ammonium salts containing long alkyl chains. Basic pesticides, on the other hand, are better absorbed in clay minerals modified with polycations. Kinetic studies and adsorption/desorption isotherms provide the parameters needed to evaluate the clay mineral’s adsorptive performance towards the pollutant target. However, the direct comparison of these parameters is complicated because the experimental conditions, the analytical techniques, the kinetic and isotherm models, and the numerical fitting method differ among the various studies. The free-energy-related Langmuir constant depends on the degree of site occupation; that is, it depends on the concentration window used to construct the adsorption isotherm and, consequently, on the analytical technique used to quantify the free concentrations. This paper reviews pesticides’ adsorption on natural and modified clay minerals and proposes guidelines for designing batch adsorption/desorption studies to obtain easily comparable and meaningful adsorption parameters. Articles should clearly describe the experimental conditions such as temperature, contact time, total concentration window, the solution to adsorbent ratio, the analytical technique, and its detection and quantification limits, besides the fitting models. Research should also evaluate the competitive effects of humic substances, colloidal inorganic particles, and ionic strength to emulate real-world adsorption experiments.
Combined Experimental and Theoretical Studies: Lattice-Dynamical Studies at High Pressures with the Help of Ab Initio Calculations
Authors: Manjón Francisco Javier , Sans Juan Ángel , Rodríguez-Hernández Placida , Muñoz Alfonso
Published: November 2021

Lattice dynamics studies are important for the proper characterization of materials, since these studies provide information on the structure and chemistry of materials via their vibrational properties. These studies are complementary to structural characterization, usually by means of electron, neutron, or X-ray diffraction measurements. In particular, Raman scattering and infrared absorption measurements are very powerful, and are the most common and easy techniques to obtain information on the vibrational modes at the Brillouin zone center. Unfortunately, many materials, like most minerals, cannot be obtained in a single crystal form, and one cannot play with the different scattering geometries in order to make a complete characterization of the Raman scattering tensor of the material. For this reason, the vibrational properties of many materials, some of them known for millennia, are poorly known even under room conditions. In this paper, we show that, although it seems contradictory, the combination of experimental and theoretical studies, like Raman scattering experiments conducted at high pressure and ab initio calculations, is of great help to obtain information on the vibrational properties of materials at different pressures, including at room pressure. The present paper does not include new experimental or computational results. Its focus is on stressing the importance of combined experimental and computational approaches to understand materials properties. For this purpose, we show examples of materials already studied in different fields, including some hot topic areas such as phase change materials, thermoelectric materials, topological insulators, and new subjects as metavalent bonding.
Infiltration Depth of Mineral Particles in Gravel-Bed Rivers
Authors: Bustamante-Penagos Natalia , Niño Yarko
Published: November 2021

This article discusses the results of an experimental study of a spill of mineral particles in gravel-bed rivers due to mining accidents. The purpose of this research is to characterize the dynamics of the fine mining particles spilled on a bed of immobilized gravel as a hyper-concentrated mixture and to experimentally characterize the infiltration phenomenon. We analyzed the type of infiltration considering the dimensionless coarse to fine particle size relationship, the dimensionless weight of the fine particles, the relative density of the particles, and the relationship between the subsurface and surface velocities, in addition to the densimetric Froude and Reynolds numbers of the fine particles. We found that the dimensionless infiltration depth is not associated with hydraulic parameters or the weight of the fine sediment spilled; however, fine sediment deposition decreases with depth, and infiltration depth may increase if subsurface flow decreases over time. Finally, a relationship of the dimensionless maximum infiltration depth with the relative density of the mining particles, the ratio of the bed sediment and the mining particles sizes, and the ratio between the subsurface and surface velocities is established.
Simulation of pH-Dependent Conformational Transitions in Membrane Proteins: The CLC-ec1 Cl−/H+ Antiporter
Authors: Kots Ekaterina , Shore Derek M. , Weinstein Harel
Published: November 2021

Intracellular transport of chloride by members of the CLC transporter family involves a coupled exchange between a Cl− anion and a proton (H+), which makes the transport function dependent on ambient pH. Transport activity peaks at pH 4.5 and stalls at neutral pH. However, a structure of the WT protein at acidic pH is not available, making it difficult to assess the global conformational rearrangements that support a pH-dependent gating mechanism. To enable modeling of the CLC-ec1 dimer at acidic pH, we have applied molecular dynamics simulations (MD) featuring a new force field modification scheme—termed an Equilibrium constant pH approach (ECpH). The ECpH method utilizes linear interpolation between the force field parameters of protonated and deprotonated states of titratable residues to achieve a representation of pH-dependence in a narrow range of physiological pH values. Simulations of the CLC-ec1 dimer at neutral and acidic pH comparing ECpH-MD to canonical MD, in which the pH-dependent protonation is represented by a binary scheme, substantiates the better agreement of the conformational changes and the final model with experimental data from NMR, cross-link and AFM studies, and reveals structural elements that support the gate-opening at pH 4.5, including the key glutamates Gluin and Gluex.
Synthesis of Purine-Based Ionic Liquids and Their Applications
Authors: Carreira Ana R. F. , Veloso Telma , Schaeffer Nicolas , Pereira Joana L. , Ventura Sónia P. M. , Rizzi Cécile , Sirieix Plénet Juliette , Passos Helena , Coutinho João A. P.
Published: November 2021

Bio-based ionic liquids (ILs) are being increasingly sought after, as they are more sustainable and eco-friendly. Purines are the most widely distributed, naturally occurring N-heterocycles, but their low water-solubility limits their application. In this work, four purines (theobromine, theophylline, xanthine, and uric acid) were combined with the cation tetrabutylammonium to synthesize bio-based ILs. The physico–chemical properties of the purine-based ILs were characterized, including their melting and decomposition temperatures and water-solubility. The ecotoxicity against the microalgae Raphidocelis subcapitata was also determined. The ILs show good thermal stability (>457 K) and an aqueous solubility enhancement ranging from 53- to 870-fold, in comparison to their respective purine percursors, unlocking new prospects for their application where aqueous solutions are demanded. The ecotoxicity of these ILs seems to be dominated by the cation, and it is similar to chloride-based IL, emphasizing that the use of natural anions does not necessarily translate to more benign ILs. The application of the novel ILs in the formation of aqueous biphasic systems (ABS), and as solubility enhancers, was also evaluated. The ILs were able to form ABS with sodium sulfate and tripotassium citrate salts. The development of thermoresponsive ABS, using sodium sulfate as a salting-out agent, was accomplished, with the ILs having different thermosensitivities. In addition, the purine-based ILs acted as solubility enhancers of ferulic acid in aqueous solution.
Don’t Overweight Weights: Evaluation of Weighting Strategies for Multi-Task Bioactivity Classification Models
Authors: Humbeck Lina , Morawietz Tobias , Sturm Noe , Zalewski Adam , Harnqvist Simon , Heyndrickx Wouter , Holmes Matthew , Beck Bernd
Published: November 2021

Machine learning models predicting the bioactivity of chemical compounds belong nowadays to the standard tools of cheminformaticians and computational medicinal chemists. Multi-task and federated learning are promising machine learning approaches that allow privacy-preserving usage of large amounts of data from diverse sources, which is crucial for achieving good generalization and high-performance results. Using large, real world data sets from six pharmaceutical companies, here we investigate different strategies for averaging weighted task loss functions to train multi-task bioactivity classification models. The weighting strategies shall be suitable for federated learning and ensure that learning efforts are well distributed even if data are diverse. Comparing several approaches using weights that depend on the number of sub-tasks per assay, task size, and class balance, respectively, we find that a simple sub-task weighting approach leads to robust model performance for all investigated data sets and is especially suited for federated learning.
Optical Activity of Metal Nanoclusters Deposited on Regular and Doped Oxide Supports from First-Principles Simulations
Authors: Sementa Luca , Stener Mauro , Fortunelli Alessandro
Published: November 2021

We report a computational study and analysis of the optical absorption processes of Ag20 and Au20 clusters deposited on the magnesium oxide (100) facet, both regular and including point defects. Ag20 and Au20 are taken as models of metal nanoparticles and their plasmonic response, MgO as a model of a simple oxide support. We consider oxide defects both on the oxygen anion framework (i.e., a neutral oxygen vacancy) and in the magnesium cation framework (i.e., replacing Mg++ with a transition metal: Cu++ or Co++). We relax the clusters’ geometries via Density-Functional Theory (DFT) and calculate the photo-absorption spectra via Time-Dependent DFT (TDDFT) simulations on the relaxed geometries. We find that the substrate/cluster interaction induces a broadening and a red-shift of the excited states of the clusters, phenomena that are enhanced by the presence of an oxygen vacancy and its localized excitations. The presence of a transition-metal dopant does not qualitatively affect the spectral profile. However, when it lies next to an oxygen vacancy for Ag20, it can strongly enhance the component of the cluster excitations perpendicular to the surface, thus favoring charge injection.
Elucidation of the Roles of Ionic Liquid in CO2 Electrochemical Reduction to Value-Added Chemicals and Fuels
Authors: Mohammed Sulafa Abdalmageed Saadaldeen , Yahya Wan Zaireen Nisa , Bustam Mohamad Azmi , Kibria Md Golam
Published: November 2021

The electrochemical reduction of carbon dioxide (CO2ER) is amongst one the most promising technologies to reduce greenhouse gas emissions since carbon dioxide (CO2) can be converted to value-added products. Moreover, the possibility of using a renewable source of energy makes this process environmentally compelling. CO2ER in ionic liquids (ILs) has recently attracted attention due to its unique properties in reducing overpotential and raising faradaic efficiency. The current literature on CO2ER mainly reports on the effect of structures, physical and chemical interactions, acidity, and the electrode–electrolyte interface region on the reaction mechanism. However, in this work, new insights are presented for the CO2ER reaction mechanism that are based on the molecular interactions of the ILs and their physicochemical properties. This new insight will open possibilities for the utilization of new types of ionic liquids. Additionally, the roles of anions, cations, and the electrodes in the CO2ER reactions are also reviewed.
Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers
Authors: Kijewska Monika , Gąszczyk Dorota , Bąchor Remigiusz , Stefanowicz Piotr , Szewczuk Zbigniew
Published: November 2021

Peptide modification by a quaternary ammonium group containing a permanent positive charge is a promising method of increasing the ionization efficiency of the analyzed compounds, making ultra-sensitive detection even at the attomolar level possible. Charge-derivatized peptides may undergo both charge remote (ChR) and charge-directed (ChD) fragmentation. A series of model peptide conjugates derivatized with N,N,N-triethyloammonium (TEA), 1-azoniabicyclo[2.2.2]octane (ABCO), 2,4,6-triphenylopyridinium (TPP) and tris(2,4,6-trimetoxyphenylo)phosphonium (TMPP) groups were analyzed by their fragmentation pathways both in collision-induced dissociation (CID) and electron-capture dissociation (ECD) mode. The effect of the fixed-charge tag type and peptide sequence on the fragmentation pathways was investigated. We found that the aspartic acid effect plays a crucial role in the CID fragmentation of TPP and TEA peptide conjugates whereas it was not resolved for the peptides derivatized with the phosphonium group. ECD spectra are mostly dominated by cn ions. ECD fragmentation of TMPP-modified peptides results in the formation of intense fragments derived from this fixed-charge tag, which may serve as reporter ion.
Plasma Exosomes of Patients with Breast and Ovarian Tumors Contain an Inactive 20S Proteasome
Authors: Yunusova Natalia , Kolegova Elena , Sereda Elena , Kolomiets Larisa , Villert Alisa , Patysheva Marina , Rekeda Irina , Grigor’eva Alina , Tarabanovskaya Natalia , Kondakova Irina , Tamkovich Svetlana
Published: November 2021

Exosomes are directly involved in governing of physiological and pathological conditions of an organism through the transfer of information from producing to receiving cells. It can be assumed that exosomes are one of the key players of tumor dissemination since they are very stable and small enough to penetrate from various tissues into biological fluids and then back, thus interacting with tissue target cells. We evaluated the enzymatic activity and the level of 20S proteasome in tissue and exosomes of healthy females (n = 39) and patients with ovarian (n = 50) and breast (n = 108) tumors to reveal the critical role of exosomal cargo in the mediation of different types of metastases. Exosomes from plasma and ascites were isolated and characterized in according to International Society for Extracellular Vesicles guidelines. The level of 20S proteasome in tissue and exosomes was determined using Western blot analysis. Chymotrypsin- and caspase-like (ChTL and CL, respectively) peptidase activities of the proteasomes were determined using fluorogenic Suc-LLVY-AMC and Cbz-LLG-AMC substrates, respectively. We observed increased levels of 20S proteasome in ovarian cancer tissue and luminal B subtype breast cancer tissue as well as in plasma exosomes from cancer patients. Moreover, the level of the 20S proteasome in plasma exosomes and ascites exosomes in patients with ovarian tumors is comparable and higher in ovarian cancer patients with low volume ascites than in patients with moderate and high-volume ascites. We also found increased ChTL and CL activities in breast cancer and ovarian cancer tissues, as well as in peritoneal metastases in ovarian cancer, while proteasomal activity in exosomes from plasma of healthy females and all patients, as well as from ascites of ovarian tumor patients were lower than detection limit of assay. Thus, regardless of the type of tumor metastasis (lymphogenous or peritoneal), the exosomes of cancer patients were characterized by an increased level of 20S proteasome, which do not exhibit enzymatic activity.
Role of Specialized Pro-Resolving Mediators in Modifying Host Defense and Decreasing Bacterial Virulence
Authors: Thornton Julianne M. , Yin Kingsley
Published: November 2021

Bacterial infection activates the innate immune system as part of the host’s defense against invading pathogens. Host response to bacterial pathogens includes leukocyte activation, inflammatory mediator release, phagocytosis, and killing of bacteria. An appropriate host response requires resolution. The resolution phase involves attenuation of neutrophil migration, neutrophil apoptosis, macrophage recruitment, increased phagocytosis, efferocytosis of apoptotic neutrophils, and tissue repair. Specialized Pro-resolving Mediators (SPMs) are bioactive fatty acids that were shown to be highly effective in promoting resolution of infectious inflammation and survival in several models of infection. In this review, we provide insight into the role of SPMs in active host defense mechanisms for bacterial clearance including a new mechanism of action in which an SPM acts directly to reduce bacterial virulence.
Preparation and Characterization of Semi-IPN Cryogels Based on Polyacrylamide and Poly(N,N-dimethylaminoethyl methacrylate); Functionalization of Carrier with Monochlorotriazinyl-β-cyclodextrin and Release Kinetics of Curcumin
Authors: Dragan Ecaterina Stela , Dinu Maria Valentina , Ghiorghita Claudiu Augustin , Lazar Maria Marinela , Doroftei Florica
Published: November 2021

Curcumin (CCM) is a natural hydrophobic polyphenol known for its numerous applications in the food industry as a colorant or jelly stabilizer, and in the pharmaceutical industry due to its anti-inflammatory, antibacterial, antioxidant, anti-cancer, and anti-Alzheimer properties. However, the large application of CCM is limited by its poor solubility in water and low stability. To enhance the bioavailability of CCM, and to protect it against the external degradation agents, a novel strategy, which consists in the preparation of semi-interpenetrating polymer networks, (s-IPNs) based on poly(N,N-dimethylaminoethyl methacrylate) entrapped in poly(acrylamide) networks, by a cryogelation technique, was developed in this work. All s-IPN cryogels were characterized by SEM, EDX, FTIR, and swelling at equilibrium as a function of pH. Functionalization of semi-IPN cryogel with monochlorotriazinyl-β-cyclodextrin (MCT-β-CD) led to IPN cryogel. The release profile of CCM from the composite cryogels was investigated at 37 °C, in pH 3. It was found that the cumulative release increased with the increase of the carrier hydrophobicity, as a result of increasing the cross-linking degree, the content and the molar mass of PDMAEMA. Fitting Higuchi, Korsmeyer–Peppas, and first order kinetic models on the CCM release profiles indicated the diffusion as the main driving force of drug release from the composite cryogels.
Kinetics and Energetics of Intramolecular Electron Transfer in Single-Point Labeled TUPS-Cytochrome c Derivatives
Authors: Khoroshyy Petro , Tenger Katalin , Chertkova Rita , Bocharova Olga , Kirpichnikov Mikhail , Borovok Natalia , Groma Géza , Dolgikh Dmitry , Kotlyar Alexander , Zimányi László
Published: November 2021

Electron transfer within and between proteins is a fundamental biological phenomenon, in which efficiency depends on several physical parameters. We have engineered a number of horse heart cytochrome c single-point mutants with cysteine substitutions at various positions of the protein surface. To these cysteines, as well as to several native lysine side chains, the photoinduced redox label 8-thiouredopyrene-1,3,6-trisulfonate (TUPS) was covalently attached. The long-lived, low potential triplet excited state of TUPS, generated with high quantum efficiency, serves as an electron donor to the oxidized heme c. The rates of the forward (from the label to the heme) and the reverse (from the reduced heme back to the oxidized label) electron transfer reactions were obtained from multichannel and single wavelength flash photolysis absorption kinetic experiments. The electronic coupling term and the reorganization energy for electron transfer in this system were estimated from temperature-dependent experiments and compared with calculated parameters using the crystal and the solution NMR structure of the protein. These results together with the observation of multiexponential kinetics strongly support earlier conclusions that the flexible arm connecting TUPS to the protein allows several shortcut routes for the electron involving through space jumps between the label and the protein surface.
Computational Investigations of a pH-Induced Structural Transition in a CTAB Solution with Toluic Acid
Authors: Wang Tingyi , Yan Hui , Lv Li , Xu Yingbiao , Zhang Lingyu , Jia Han
Published: November 2021

In this work, molecular dynamics simulations were performed to study the pH-induced structural transitions for a CTAB/p-toluic acid solution. Spherical and cylindrical micelles were obtained for aqueous surfactants at pH 2 and 7, respectively, which agrees well with the experimental observations. The structural properties of two different micelles were analyzed through the density distributions of components and the molecular orientations of CTA+ and toluic acid inside the micelles. It was found that the bonding interactions between CTA+ and toluic in spherical and cylindrical micelles are very different. Almost all the ionized toluic acid (PTA−) in the solution at pH 7 was solubilized into the micelles, and it was located in the CTA+ headgroups region. Additionally, the bonding between surfactant CTA+ and PTA− was very tight due to the electrostatic interactions. The PTA− that penetrated into the micelles effectively screened the electrostatic repulsion among the cationic headgroups, which is considered to be crucial for maintaining the cylindrical micellar shape. As the pH decreased, the carboxyl groups were protonated. The hydration ability of neutral carboxyl groups weakened, resulting in deeper penetration into the micelles. Meanwhile, their bonding interactions with surfactant headgroups also weakened. Accompanied by the strengthen of electrostatic repulsion among the positive headgroups, the cylindrical micelle was broken into spherical micelles. Our work provided an atomic-level insights into the mechanism of pH-induced structural transitions of a CTAB/p-toluic solution, which is expected to be useful for further understanding the aggregate behavior of mixed cationic surfactants and aromatic acids.
The Ability of Near Infrared (NIR) Spectroscopy to Predict Functional Properties in Foods: Challenges and Opportunities
Authors: Cozzolino Daniel
Published: November 2021

Near infrared (NIR) spectroscopy is considered one of the main routine analytical methods used by the food industry. This technique is utilised to determine proximate chemical compositions (e.g., protein, dry matter, fat and fibre) of a wide range of food ingredients and products. Novel algorithms and new instrumentation are allowing the development of new applications of NIR spectroscopy in the field of food science and technology. Specifically, several studies have reported the use of NIR spectroscopy to evaluate or measure functional properties in both food ingredients and products in addition to their chemical composition. This mini-review highlights and discussed the applications, challenges and opportunities that NIR spectroscopy offers to target the quantification and measurement of food functionality in dairy and cereals.
Design, Synthesis, and Evaluation of Near-Infrared Fluorescent Molecules Based on 4H-1-Benzopyran Core
Authors: Wang Shuting , Zhu Shulei , Tanzeng Yawen , Zhang Yuexing , Li Chuchu , Ma Mingliang , Lu Wei
Published: November 2021

A series of novel fluorescent 4H-1-benzopyrans was designed and developed as near-infrared fluorescent molecules with a compact donor–acceptor-donor architecture. Spectral intensity of the fluorescent molecules M-1, M-2, M-3 varied significantly with the increasing polarities of solvents, where M-3 showed high viscosity sensitivity in glycerol-ethanol system with a 3-fold increase in emission intensity. Increasing concentrations of compound M-3 to 5% BSA in PBS elicited a 4-fold increase in fluorescence intensity, exhibiting a superior environmental sensitivity. Furthermore, the in vitro cellular uptake behavior and CLSM assay of cancer cell lines demonstrated that M-3 could easily enter the cell nucleus and bind to proteins with low toxicity. Therefore, the synthesized near-infrared fluorescent molecules could provide a new direction for the development of optical imaging probes and potential further drugs.