bluuebunny/crossref_metadata_2025 huggingface dataset:
Vibrational Dynamics in crystalline 4-(dimethylamino) benzaldehyde: Inelastic Neutron Scattering and Periodic DFT Study
Authors: Nolasco Mariela M. , Ribeiro-Claro Paulo J. A. , Vaz Pedro D.
Published: January 2022

The structure and dynamics of crystalline 4-(dimethylamino) benzaldehyde, 4DMAB, are assessed through INS spectroscopy combined with periodic DFT calculations. The excellent agreement between experimental and calculated spectra is the basis for a reliable assignment of INS bands. The external phonon modes of crystalline 4DMAB are quite well described by the simulated spectrum, as well as the modes involving low-frequency molecular vibrations. Crystal field splitting is predicted and observed for the modes assigned to the dimethylamino group. Concerning the torsional motion of methyl groups, four individual bands are identified and assigned to specific methyl groups in the asymmetric unit. The torsional frequencies of the four methyl groups in the asymmetric unit fall in a region of ca. 190 ± 20 cm−1, close to the range of values observed for methyl groups bonding to unsaturated carbon atoms. The hybridization state of the X atom in X-CH3 seems to play a key role in determining the methyl torsional frequency.
Modeling of the Point Defect Migration across the AlN/GaN Interfaces—Ab Initio Study
Authors: Hrytsak Roman , Kempisty Pawel , Grzanka Ewa , Leszczynski Michal , Sznajder Malgorzata
Published: January 2022

The formation and diffusion of point defects have a detrimental impact on the functionality of devices in which a high quality AlN/GaN heterointerface is required. The present paper demonstrated the heights of the migration energy barriers of native point defects throughout the AlN/GaN heterointerface, as well as the corresponding profiles of energy bands calculated by means of density functional theory. Both neutral and charged nitrogen, gallium, and aluminium vacancies were studied, as well as their complexes with a substitutional III-group element. Three diffusion mechanisms, that is, the vacancy mediated, direct interstitial, and indirect ones, in bulk AlN and GaN crystals, as well at the AlN/GaN heterointerface, were taken into account. We showed that metal vacancies migrated across the AlN/GaN interface, overcoming a lower potential barrier than that of the nitrogen vacancy. Additionally, we demonstrated the effect of the inversion of the electric field in the presence of charged point defects VGa3− and VAl3− at the AlN/GaN heterointerface, not reported so far. Our findings contributed to the issues of structure design, quality control, and improvement of the interfacial abruptness of the AlN/GaN heterostructures.
Modeling the Hydrogen Redistribution at the Grain Boundary of Misoriented Bicrystals in Austenite Stainless Steel
Authors: Yang Fuqiang , Yan Tao , Zhang Wenjuan , Zhang Haibing , Zhao Lingyan
Published: January 2022

Hydrogen embrittlement, as one of the major concerns for austenitic stainless steel, is closely linked to the diffusion of hydrogen through the grain boundary of materials. The phenomenon is still not well understood yet, especially the full interaction between hydrogen diffusion and the misorientation of the grains. This work aimed at the development of a robust numerical strategy to model the full coupling of the hydrogen diffusion and the anisotropic behavior of crystals in 316 stainless steel. A constitutive model, which allows easy incorporation of crystal orientation, various loading conditions, and arbitrary model geometries, was established by using the finite element package ABAQUS. The study focuses on three different bicrystal models composed of misoriented crystals, and the results indicate that the redistribution of hydrogen is significant closely to the grain boundary, and the redistribution is driven by the hydrostatic pressure caused by the misorientation of two neighboring grains. A higher elastic modulus ratio along the tensile direction will lead to a higher hydrogen concentration difference in the two grains equidistant from the grain boundary. The hydrogen concentration shows a high value in the crystal along the direction with stiff elastic modulus. Moreover, there exists a large hydrogen concentration gradient in a narrow region very close to the grain boundary to balance the concentration difference of the neighboring grains.
Green Synthesis of Stable Spherical Monodisperse Silver Nanoparticles Using a Cell-Free Extract of Trichoderma reesei
Authors: Gemishev Orlin , Panayotova Marinela , Gicheva Gospodinka , Mintcheva Neli
Published: January 2022

In the current study, a green method for the preparation of silver nanoparticles (AgNPs) is presented as an alternative to conventional chemical and physical approaches. A biomass of Trichoderma reesei (T. reesei) fungus was used as a green and renewable source of reductase enzymes and metabolites, which are capable of transforming Ag+ ions into AgNPs with a small size (mainly 2–6 nm) and narrow size distribution (2–25 nm). Moreover, extracellular biosynthesis was carried out with a cell-free water extract (CFE) of T. reesei, which allows for facile monitoring of the bioreduction process using UV–Vis spectroscopy and investigation of the effect of experimental conditions on the transformation of Ag+ ions into AgNPs, as well as the simple isolation of as-prepared AgNPs for the study of their size, morphology and antibacterial properties. In continuation to our previous results about the influence of media on T. reesei cultivation, the amount of biomass used for CFE preparation and the concentration of Ag+ ion solution, herein, we present the impact of temperature (4, 20, 30 and 40 °C), agitation and time duration on the biosynthesis of AgNPs and their properties. A high stability of AgNPs in aqueous colloids was observed and attributed to the capping effect of the biomolecules as shown by the zeta potential (−49.0/−51.4 mV) and confirmed by the hydrodynamic size of 190.8/116.8 nm of AgNPs.
Seeing Structural Mechanisms of Optimized Piezoelectric and Thermoelectric Bulk Materials through Structural Defect Engineering
Authors: Zhang Yang , Qu Wanbo , Peng Guyang , Zhang Chenglong , Liu Ziyu , Liu Juncheng , Li Shurong , Wu Haijun , Meng Lingjie , Gao Lumei
Published: January 2022

Aberration-corrected scanning transmission electron microscopy (AC-STEM) has evolved into the most powerful characterization and manufacturing platform for all materials, especially functional materials with complex structural characteristics that respond dynamically to external fields. It has become possible to directly observe and tune all kinds of defects, including those at the crucial atomic scale. In-depth understanding and technically tailoring structural defects will be of great significance for revealing the structure-performance relation of existing high-property materials, as well as for foreseeing paths to the design of high-performance materials. Insights would be gained from piezoelectrics and thermoelectrics, two representative functional materials. A general strategy is highlighted for optimizing these functional materials’ properties, namely defect engineering at the atomic scale.
Durability Performance of Self-Compacting Concrete Containing Crumb Rubber, Fly Ash and Calcium Carbide Waste
Authors: Kelechi Sylvia E. , Adamu Musa , Mohammed Abubakar , Ibrahim Yasser E. , Obianyo Ifeyinwa I.
Published: January 2022

Waste tire disposal continues to pose a threat to the environment due to its non-biodegradable nature. Therefore, some means of managing waste tires include grinding them to crumb rubber (CR) sizes and using them as a partial replacement to fine aggregate in concrete. However, the use of CR has a series of advantages, but its major disadvantage is strength reduction. This leads to the utilization of calcium carbide waste (CCW) to mitigate the negative effect of CR in self-compacting concrete (SCC). This study investigates the durability properties of SCC containing CR modified using fly ash and CCW. The durability properties considered are water absorption, acid attack, salt resistance, and elevated temperature of the mixes. The experiment was conducted for mixes with no-fly ash content and their replica mixes containing fly ash to replace 40% of the cement. In the mixes, CR was used to partially replace fine aggregate in proportions of 0%, 10%, and 20% by volume, and CCW was used as a partial replacement to cement at 0%, 5%, and 10% by volume. The results indicate that the mixes containing fly ash had higher resistance to acid (H2SO4) and salt (MgSO4), with up to 23% resistance observed when compared to the mix containing no fly ash. In addition, resistance to acid attack decreased with the increase in the replacement of fine aggregate with CR. The same principle applied to the salt attack scenario, although the rate was more rapid with the acid than the salt. The results obtained from heating indicate that the weight loss was reduced slightly with the increase in CCW, and was increased with the increase in CR and temperature. Similarly, the compressive strength was observed to slightly increase at room temperature (27 °C) and the greatest loss in compressive strength was observed between the temperature of 300 and 400 °C. However, highest water absorption, of 2.83%, was observed in the mix containing 20% CR, and 0% CCW, while the lowest water absorption, of 1.68%, was found in the mix with 0% CR, 40% fly ash, and 10% CCW. In conclusion, fly ash is recommended for concrete structures immersed in water, acid, or salt in sulphate- and magnesium-prone areas; conversely, fly ash and CR reduce the resistance of SCC to heat beyond 200 °C.
Sonneradon A Extends Lifespan of Caenorhabditis elegans by Modulating Mitochondrial and IIS Signaling Pathways
Authors: Jiang Shu , Jiang Cui-Ping , Cao Pei , Liu Yong-Hong , Gao Cheng-Hai , Yi Xiang-Xi
Published: January 2022

Aging is related to the lowered overall functioning and increased risk for various age-related diseases in humans. Sonneradon A (SDA), a new compound first extracted from the edible fruits of mangrove Sonneratia apetala, showed remarkable antiaging activity. However, the role of SDA in antiaging remains unclear. In this article, we studied the function of SDA in antiaging by using the animal model Caenorhabditis elegans. Results showed that SDA inhibited production of reactive oxygen species (ROS) by 53%, and reduced the accumulation of aging markers such as lipids and lipofuscins. Moreover, SDA also enhanced the innate immune response to Pseudomonas aeruginosa infection. Genetic analysis of a series of mutants showed that SDA extended the lifespan of the mutants of eat-2 and glp-1. Together, this effect may be related to the enhanced resistance to oxidative stress via mitochondrial and insulin/insulin-like growth factor-1 signaling (IIS) pathways. The results of this study provided new evidence for an antiaging effect of SDA in C. elegans, as well as insights into the implication of antiaging activity of SDA in higher organisms.
Marine Collagen: A Promising Biomaterial for Wound Healing, Skin Anti-Aging, and Bone Regeneration
Authors: Geahchan Sarah , Baharlouei Parnian , Rahman Azizur
Published: January 2022

Marine organisms harbor numerous bioactive substances that can be utilized in the pharmaceutical and cosmetic industries. Scientific research on various applications of collagen extracted from these organisms has become increasingly prevalent. Marine collagen can be used as a biomaterial because it is water soluble, metabolically compatible, and highly accessible. Upon review of the literature, it is evident that marine collagen is a versatile compound capable of healing skin injuries of varying severity, as well as delaying the natural human aging process. From in vitro to in vivo experiments, collagen has demonstrated its ability to invoke keratinocyte and fibroblast migration as well as vascularization of the skin. Additionally, marine collagen and derivatives have proven beneficial and useful for both osteoporosis and osteoarthritis prevention and treatment. Other bone-related diseases may also be targeted by collagen, as it is capable of increasing bone mineral density, mineral deposition, and importantly, osteoblast maturation and proliferation. In this review, we demonstrate the advantages of marine collagen over land animal sources and the biomedical applications of marine collagen related to bone and skin damage. Finally, some limitations of marine collagen are briefly discussed.
Proposal of an Algorithm to Early Detect Attenuated Type I Mucopolysaccharidosis (MPS Ia) among Children with Growth Abnormalities
Authors: Baronio Federico , Zucchini Stefano , Zulian Francesco , Salerno Mariacarolina , Parini Rossella , Cattoni Alessandro , Deodato Federica , Gaeta Alberto , Bizzarri Carla , Gasperini Serena , Pession Andrea
Published: January 2022

Background and Objectives: Diagnostic delay is common in attenuated Mucopolysaccharidosis Type I (MPS Ia) due to the rarity of the disease and the variability of clinical presentation. Short stature and impaired growth velocity are frequent findings in MPS Ia, but they rarely raise suspicion as paediatric endocrinologists are generally poorly trained to detect earlier and milder clinical signs of this condition. Materials and Methods: Following a consensus-based methodology, a multidisciplinary panel including paediatric endocrinologists, paediatricians with expertise in metabolic disorders, radiologists, and rheumatologists shared their experience on a possible clinical approach to the diagnosis of MPS Ia in children with short stature or stunted growth. Results: The result was the formation of an algorithm that illustrates how to raise the suspicion of MPS Ia in a patient older than 5 years with short stature and suggestive clinical signs. Conclusion: The proposed algorithm may represent a useful tool to improve the awareness of paediatric endocrinologists and reduce the diagnostic delay for patients with MPS Ia.
Low Cycle Fatigue Performance of Additively Processed and Heat-Treated Ti-6Al-7Nb Alloy for Biomedical Applications
Authors: Hein Maxwell , Kokalj David , Lopes Dias Nelson Filipe , Stangier Dominic , Oltmanns Hilke , Pramanik Sudipta , Kietzmann Manfred , Hoyer Kay-Peter , Meißner Jessica , Tillmann Wolfgang , Schaper Mirko
Published: January 2022

In biomedical engineering, laser powder bed fusion is an advanced manufacturing technology, which enables, for example, the production of patient-customized implants with complex geometries. Ti-6Al-7Nb shows promising improvements, especially regarding biocompatibility, compared with other titanium alloys. The biocompatible features are investigated employing cytocompatibility and antibacterial examinations on Al2O3-blasted and untreated surfaces. The mechanical properties of additively manufactured Ti-6Al-7Nb are evaluated in as-built and heat-treated conditions. Recrystallization annealing (925 °C for 4 h), β annealing (1050 °C for 2 h), as well as stress relieving (600 °C for 4 h) are applied. For microstructural investigation, scanning and transmission electron microscopy are performed. The different microstructures and the mechanical properties are compared. Mechanical behavior is determined based on quasi-static tensile tests and strain-controlled low cycle fatigue tests with total strain amplitudes εA of 0.35%, 0.5%, and 0.8%. The as-built and stress-relieved conditions meet the mechanical demands for the tensile properties of the international standard ISO 5832-11. Based on the Coffin–Manson–Basquin relation, fatigue strength and ductility coefficients, as well as exponents, are determined to examine fatigue life for the different conditions. The stress-relieved condition exhibits, overall, the best properties regarding monotonic tensile and cyclic fatigue behavior.
Using Plane Strain Compression Test to Evaluate the Mechanical Behavior of Magnesium Processed by HPT
Authors: Carvalho Amanda P. , Reis Leonardo M. , Pinheiro Ravel P. R. P. , Pereira Pedro Henrique R. , Langdon Terence G. , Figueiredo Roberto B.
Published: January 2022

There is a great interest in improving mechanical testing of small samples produced in the laboratory. Plane strain compression is an effective test in which the workpiece is a thin sheet. This provides great potential for testing samples produced by high-pressure torsion. Thus, a custom tool was designed with the aim to test 10 mm diameter discs processed by this technique. Finite element analysis is used to evaluate the deformation zone, stress and strain distribution, and the accuracy in the estimation of stress–strain curves. Pure magnesium and a magnesium alloy processed by high-pressure torsion are tested using this custom-made tool. The trends observed in strength and ductility agree with trends reported in the literature for these materials.
Predicting Cutting Force and Primary Shear Behavior in Micro-Textured Tools Assisted Machining of AISI 630: Numerical Modeling and Taguchi Analysis
Authors: Ali Shafahat , Abdallah Said , Pervaiz Salman
Published: January 2022

The cutting tool heats up during the cutting of high-performance super alloys and it negatively affects the life of the cutting tool. Improved tool life can enhance both the machinability and sustainability of the cutting process. To improve the tool life preferably cutting fluids are utilized. However, the majority of cutting fluids are non-biodegradable in nature and pose harmful threats to the environment. It has been established in the metal cutting literature that introducing microgrooves at the cutting tool rake face can significantly reduce the coefficient of friction (COF). Reduction in the COF promotes anti-adhesive behavior that improves the tool life. The current study numerically investigates the orthogonal cutting process of AISI 630 Stainless Steel using different micro grooved cutting tools. Results of the numerical simulations point to the positive influence of micro grooves on tool life. The results of the main effects found that the cutting temperature was decreased by approximately 10% and 7% with rectangular and triangular micro grooved tools, respectively. Over machining performance indicated that rectangular micro groove tools provided comparatively better performance.
Flow and Heat Transfer Performances of Liquid Metal Based Microchannel Heat Sinks under High Temperature Conditions
Authors: Wu Tao , Wang Lizhi , Tang Yicun , Yin Chao , Li Xiankai
Published: January 2022

Developments in applications such as rocket nozzles, miniature nuclear reactors and solar thermal generation pose high-density heat dissipation challenges. In these applications, a large amount heat must be removed in a limited space under high temperature. In order to handle this kind of cooling problem, this paper proposes liquid metal-based microchannel heat sinks. Using a numerical method, the flow and heat transfer performances of liquid metal-based heat sinks with different working fluid types, diverse microchannel cross-section shapes and various inlet velocities were studied. By solving the 3-D steady and conjugate heat transfer model, we found that among all the investigated cases, lithium and circle were the most appropriate choices for the working fluid and microchannel cross-section shape, respectively. Moreover, inlet velocity had a great influence on the flow and heat transfer performances. From 1 m/s to 9 m/s, the pressure drop increased as much as 65 times, and the heat transfer coefficient was enhanced by about 74.35%.
Compact Model for Bipolar and Multilevel Resistive Switching in Metal-Oxide Memristors
Authors: Ryndin Eugeny , Andreeva Natalia , Luchinin Victor
Published: January 2022

The article presents the results of the development and study of a combined circuitry (compact) model of thin metal oxide films based memristive elements, which makes it possible to simulate both bipolar switching processes and multilevel tuning of the memristor conductivity taking into account the statistical variability of parameters for both device-to-device and cycle-to-cycle switching. The equivalent circuit of the memristive element and the equation system of the proposed model are considered. The software implementation of the model in the MATLAB has been made. The results of modeling static current-voltage characteristics and transient processes during bipolar switching and multilevel turning of the conductivity of memristive elements are obtained. A good agreement between the simulation results and the measured current-voltage characteristics of memristors based on TiOx films (30 nm) and bilayer TiO2/Al2O3 structures (60 nm/5 nm) is demonstrated.
Fabrication of 2-D Capacitive Micromachined Ultrasonic Transducer (CMUT) Array through Silicon Wafer Bonding
Authors: Wang Ziyuan , He Changde , Zhang Wendong , Li Yifan , Gao Pengfei , Meng Yanan , Zhang Guojun , Yang Yuhua , Wang Renxin , Cui Jiangong , Wang Hongliang , Zhang Binzhen , Ren Yongfeng , Zhen Guoyong , Jiao Xinquan , Zhang Sai
Published: January 2022

Capacitive micromachined ultrasound transducers (CMUTs) have broad application prospects in medical imaging, flow monitoring, and nondestructive testing. CMUT arrays are limited by their fabrication process, which seriously restricts their further development and application. In this paper, a vacuum-sealed device for medical applications is introduced, which has the advantages of simple manufacturing process, no static friction, repeatability, and high reliability. The CMUT array suitable for medical imaging frequency band was fabricated by a silicon wafer bonding technology, and the adjacent array devices were isolated by an isolation slot, which was cut through the silicon film. The CMUT device fabricated following this process is a 4 × 16 array with a single element size of 1 mm × 1 mm. Device performance tests were conducted, where the center frequency of the transducer was 3.8 MHz, and the 6 dB fractional bandwidth was 110%. The static capacitance (29.4 pF) and center frequency (3.78 MHz) of each element of the array were tested, and the results revealed that the array has good consistency. Moreover, the transmitting and receiving performance of the transducer was evaluated by acoustic tests, and the receiving sensitivity was −211 dB @ 3 MHz, −213 dB @ 4 MHz. Finally, reflection imaging was performed using the array, which provides certain technical support for the research of two-dimensional CMUT arrays in the field of 3D ultrasound imaging.
Paleoenvironment of the Lower Ordovician Meitan Formation in the Sichuan Basin and Adjacent Areas, China
Authors: Yang Meihua , Zuo Yinhui , Fu Xiaodong , Qiu Lei , Li Wenzheng , Zhang Jianyong , Zheng Ziyun , Zhang Jiazhen
Published: January 2022

The quality of hydrocarbon source rocks is affected by the sedimentary paleoenvironment. A paleoenvironment with anoxia and a high paleoproductivity is beneficial to source rocks. The paleoenvironment of the Lower Ordovician Meitan Formation of the Sichuan Basin and its adjacent areas is lacking, restricting the oil and gas exploration of the Ordovician in the Sichuan Basin and its adjacent areas. In this paper, the content of major and trace elements of 50 samples was tested to clarify the paleoenvironment of the Meitan Formation. The paleoclimate, paleosalinity, paleoredox, and paleoproductivity during the deposition of the Meitan Formation were analyzed. The control effect of the paleoenvironment on the development of source rocks was clarified, and the favorable paleoenvironment for source rock development was pointed out. The results show that the paleoenvironment of the Meitan Formation has the following characteristics: humidity, brackish water, oxygen depletion, anoxia environment, and high paleoproductivity. These characteristics are conducive to the development of poor and moderate source rocks. The source rocks of the Meitan Formation were developed in the north, west, and south of the Sichuan Basin and its adjacent areas. The organic matter of the source rocks is mainly typed II1 kerogen, and the quality is evaluated as poor-medium source rocks having the potential of generating oil and gas. This study can provide fundamental parameters for the further exploration of Ordovician petroleum.
Thermodynamically Stable Cationic Dimers in Carboxyl-Functionalized Ionic Liquids: The Paradoxical Case of “Anti-Electrostatic” Hydrogen Bonding
Authors: Al-Sheakh Loai , Fritsch Sebastian , Appelhagen Andreas , Villinger Alexander , Ludwig Ralf
Published: January 2022

We show that carboxyl-functionalized ionic liquids (ILs) form doubly hydrogen-bonded cationic dimers (c+=c+) despite the repulsive forces between ions of like charge and competing hydrogen bonds between cation and anion (c+–a−). This structural motif as known for formic acid, the archetype of double hydrogen bridges, is present in the solid state of the IL 1−(carboxymethyl)pyridinium bis(trifluoromethylsulfonyl)imide [HOOC−CH2−py][NTf2]. By means of quantum chemical calculations, we explored different hydrogen-bonded isomers of neutral (HOOC–(CH2)n–py+)2(NTf2−)2, single-charged (HOOC–(CH2)n–py+)2(NTf2−), and double-charged (HOOC– (CH2)n−py+)2 complexes for demonstrating the paradoxical case of “anti-electrostatic” hydrogen bonding (AEHB) between ions of like charge. For the pure doubly hydrogen-bonded cationic dimers (HOOC– (CH2)n−py+)2, we report robust kinetic stability for n = 1–4. At n = 5, hydrogen bonding and dispersion fully compensate for the repulsive Coulomb forces between the cations, allowing for the quantification of the two equivalent hydrogen bonds and dispersion interaction in the order of 58.5 and 11 kJmol−1, respectively. For n = 6–8, we calculated negative free energies for temperatures below 47, 80, and 114 K, respectively. Quantum cluster equilibrium (QCE) theory predicts the equilibria between cationic monomers and dimers by considering the intermolecular interaction between the species, leading to thermodynamic stability at even higher temperatures. We rationalize the H-bond characteristics of the cationic dimers by the natural bond orbital (NBO) approach, emphasizing the strong correlation between NBO-based and spectroscopic descriptors, such as NMR chemical shifts and vibrational frequencies.
Synthesis and Characterization of New Boron Compounds Using Reaction of Diazonium Tetraphenylborate with Enaminoamides
Authors: Svobodová Markéta , Svoboda Jan , Li Bing-Han , Bertolasi Valerio , Socha Luboš , Sedlák Miloš , Marek Lukáš
Published: January 2022

A family of oxazaborines, diazaborinones, triazaborines, and triazaborinones was prepared by reaction of polarized ethylenes, such as β-enaminoamides, with 4-methylbenzenediazonium tetraphenylborates. The reaction conditions (stirring in CH2Cl2 at room temperature (Method A) or stirring with CH3COONa in CH2Cl2 at room temperature (Method B) or refluxing in the CH2Cl2/toluene mixture (Method C)) controlled the formation and relative content of these compounds in the reaction mixtures from one to three products. Substituted oxazaborines gradually rearranged into diazaborinones at 250 °C. The prepared compounds were characterized by 1H NMR, 13C NMR, IR, and UV–Vis spectroscopy, HRMS, or microanalysis. The structure of individual compounds was confirmed by 11B NMR, 15N NMR, 1D NOESY, and X-ray analysis. The mechanism of reaction of enaminoamides with 4-methylbenzenediazonium tetraphenylborate was proposed.
Alternative Extraction and Downstream Purification Processes for Anthocyanins
Authors: Nunes Ana N. , Borges Alexandra , Matias Ana A. , Bronze Maria Rosário , Oliveira Joana
Published: January 2022

Anthocyanins are natural pigments displaying different attractive colors ranging from red, violet, to blue. These pigments present health benefits that increased their use in food, nutraceuticals, and the cosmetic industry. However, anthocyanins are mainly extracted through conventional methods that are time-consuming and involve the use of organic solvents. Moreover, the chemical diversity of the obtained complex extracts make the downstream purification step challenging. Therefore, the growing demand of these high-value pigments has stimulated the interest in designing new, safe, cost-effective, and tunable strategies for their extraction and purification. The current review focuses on the potential application of compressed fluid-based (such as subcritical and supercritical fluid extraction and pressurized liquid extraction) and deep eutectic solvents-based extraction methods for the recovery of anthocyanins. In addition, an updated review of the application of counter-current chromatography for anthocyanins purification is provided as a faster and cost-effective alternative to preparative-scale HPLC.
The Impact of a Graded Maximal Exercise Protocol on Exhaled Volatile Organic Compounds: A Pilot Study
Authors: Heaney Liam M. , Kang Shuo , Turner Matthew A. , Lindley Martin R. , Thomas C. L. Paul
Published: January 2022

Exhaled volatile organic compounds (VOCs) are of interest due to their minimally invasive sampling procedure. Previous studies have investigated the impact of exercise, with evidence suggesting that breath VOCs reflect exercise-induced metabolic activity. However, these studies have yet to investigate the impact of maximal exercise to exhaustion on breath VOCs, which was the main aim of this study. Two-litre breath samples were collected onto thermal desorption tubes using a portable breath collection unit. Samples were collected pre-exercise, and at 10 and 60 min following a maximal exercise test (VO2MAX). Breath VOCs were analysed by thermal desorption-gas chromatography-mass spectrometry using a non-targeted approach. Data showed a tendency for reduced isoprene in samples at 10 min post-exercise, with a return to baseline by 60 min. However, inter-individual variation meant differences between baseline and 10 min could not be confirmed, although the 10 and 60 min timepoints were different (p = 0.041). In addition, baseline samples showed a tendency for both acetone and isoprene to be reduced in those with higher absolute VO2MAX scores (mL(O2)/min), although with restricted statistical power. Baseline samples could not differentiate between relative VO2MAX scores (mL(O2)/kg/min). In conclusion, these data support that isoprene levels are dynamic in response to exercise.
Pseudomonas Lipopeptide-Mediated Biocontrol: Chemotaxonomy and Biological Activity
Authors: Oni Feyisara Eyiwumi , Esmaeel Qassim , Onyeka Joseph Tobias , Adeleke Rasheed , Jacquard Cedric , Clement Christophe , Gross Harald , Ait Barka Essaid , Höfte Monica
Published: January 2022

Pseudomonas lipopeptides (Ps-LPs) play crucial roles in bacterial physiology, host–microbe interactions and plant disease control. Beneficial LP producers have mainly been isolated from the rhizosphere, phyllosphere and from bulk soils. Despite their wide geographic distribution and host range, emerging evidence suggests that LP-producing pseudomonads and their corresponding molecules display tight specificity and follow a phylogenetic distribution. About a decade ago, biocontrol LPs were mainly reported from the P. fluorescens group, but this has drastically advanced due to increased LP diversity research. On the one hand, the presence of a close-knit relationship between Pseudomonas taxonomy and the molecule produced may provide a startup toolbox for the delineation of unknown LPs into existing (or novel) LP groups. Furthermore, a taxonomy–molecule match may facilitate decisions regarding antimicrobial activity profiling and subsequent agricultural relevance of such LPs. In this review, we highlight and discuss the production of beneficial Ps-LPs by strains situated within unique taxonomic groups and the lineage-specificity and coevolution of this relationship. We also chronicle the antimicrobial activity demonstrated by these biomolecules in limited plant systems compared with multiple in vitro assays. Our review further stresses the need to systematically elucidate the roles of diverse Ps-LP groups in direct plant–pathogen interactions and in the enhancement of plant innate immunity.
Preparation and Electrochemical Performance of Three-Dimensional Vertically Aligned Graphene by Unidirectional Freezing Method
Authors: Xia Peng , Zhang Zhenwang , Tang Zhihong , Xue Yuhua , Li Jing , Yang Guangzhi
Published: January 2022

Three-dimensional vertically aligned graphene (3DVAG) was prepared by a unidirectional freezing method, and its electrochemical performances were evaluated as electrode materials for zinc−ion hybrid supercapacitors (ZHSCs). The prepared 3DVAG has a vertically ordered channel structure with a diameter of about 20−30 μm and a length stretching about hundreds of microns. Compared with the random structure of reduced graphene oxide (3DrGO), the vertical structure of 3DVAG in a three−electrode system showed higher specific capacitance, faster ion diffusion, and better rate performance. The specific capacitance of 3DVAG reached 66.6 F·g−1 and the rate performance reached 92.2%. The constructed 3DVAG zinc−ion hybrid supercapacitor also showed excellent electrochemical performance. It showed good capacitance retention up to 94.6% after 3000 cycles at the current density of 2 A·g−1.
Anti-Electrostatic Pi-Hole Bonding: How Covalency Conquers Coulombics
Authors: Weinhold Frank
Published: January 2022

Intermolecular bonding attraction at π-bonded centers is often described as “electrostatically driven” and given quasi-classical rationalization in terms of a “pi hole” depletion region in the electrostatic potential. However, we demonstrate here that such bonding attraction also occurs between closed-shell ions of like charge, thereby yielding locally stable complexes that sharply violate classical electrostatic expectations. Standard DFT and MP2 computational methods are employed to investigate complexation of simple pi-bonded diatomic anions (BO−, CN−) with simple atomic anions (H−, F−) or with one another. Such “anti-electrostatic” anion–anion attractions are shown to lead to robust metastable binding wells (ranging up to 20–30 kcal/mol at DFT level, or still deeper at dynamically correlated MP2 level) that are shielded by broad predissociation barriers (ranging up to 1.5 Å width) from long-range ionic dissociation. Like-charge attraction at pi-centers thereby provides additional evidence for the dominance of 3-center/4-electron (3c/4e) nD-π*AX interactions that are fully analogous to the nD-σ*AH interactions of H-bonding. Using standard keyword options of natural bond orbital (NBO) analysis, we demonstrate that both n-σ* (sigma hole) and n-π* (pi hole) interactions represent simple variants of the essential resonance-type donor-acceptor (Bürgi–Dunitz-type) attraction that apparently underlies all intermolecular association phenomena of chemical interest. We further demonstrate that “deletion” of such π*-based donor-acceptor interaction obliterates the characteristic Bürgi–Dunitz signatures of pi-hole interactions, thereby establishing the unique cause/effect relationship to short-range covalency (“charge transfer”) rather than envisioned Coulombic properties of unperturbed monomers.
A Promising Thermodynamic Study of Hole Transport Materials to Develop Solar Cells: 1,3-Bis(N-carbazolyl)benzene and 1,4-Bis(diphenylamino)benzene
Authors: Mentado-Morales Juan , Ximello-Hernández Arturo , Salinas-Luna Javier , Freitas Vera L. S. , Ribeiro da Silva Maria D. M. C.
Published: January 2022

The thermochemical study of the 1,3-bis(N-carbazolyl)benzene (NCB) and 1,4-bis(diphenylamino)benzene (DAB) involved the combination of combustion calorimetric (CC) and thermogravimetric techniques. The molar heat capacities over the temperature range of (274.15 to 332.15) K, as well as the melting temperatures and enthalpies of fusion were measured for both compounds by differential scanning calorimetry (DSC). The standard molar enthalpies of formation in the crystalline phase were calculated from the values of combustion energy, which in turn were measured using a semi-micro combustion calorimeter. From the thermogravimetric analysis (TGA), the rate of mass loss as a function of the temperature was measured, which was then correlated with Langmuir’s equation to derive the vaporization enthalpies for both compounds. From the combination of experimental thermodynamic parameters, it was possible to derive the enthalpy of formation in the gaseous state of each of the title compounds. This parameter was also estimated from computational studies using the G3MP2B3 composite method. To prove the identity of the compounds, the 1H and 13C spectra were determined by nuclear magnetic resonance (NMR), and the Raman spectra of the study compounds of this work were obtained.
Aptamers: Potential Diagnostic and Therapeutic Agents for Blood Diseases
Authors: Aljohani Maher M. , Cialla-May Dana , Popp Jürgen , Chinnappan Raja , Al-Kattan Khaled , Zourob Mohammed
Published: January 2022

Aptamers are RNA/DNA oligonucleotide molecules that specifically bind to a targeted complementary molecule. As potential recognition elements with promising diagnostic and therapeutic applications, aptamers, such as monoclonal antibodies, could provide many treatment and diagnostic options for blood diseases. Aptamers present several superior features over antibodies, including a simple in vitro selection and production, ease of modification and conjugation, high stability, and low immunogenicity. Emerging as promising alternatives to antibodies, aptamers could overcome the present limitations of monoclonal antibody therapy to provide novel diagnostic, therapeutic, and preventive treatments for blood diseases. Researchers in several biomedical areas, such as biomarker detection, diagnosis, imaging, and targeted therapy, have widely investigated aptamers, and several aptamers have been developed over the past two decades. One of these is the pegaptanib sodium injection, an aptamer-based therapeutic that functions as an anti-angiogenic medicine, and it is the first aptamer approved by the U.S. Food and Drug Administration (FDA) for therapeutic use. Several other aptamers are now in clinical trials. In this review, we highlight the current state of aptamers in the clinical trial program and introduce some promising aptamers currently in pre-clinical development for blood diseases.
Computational Estimation of the Acidities of Pyrimidines and Related Compounds
Authors: Holt Rachael A. , Seybold Paul G.
Published: January 2022

Pyrimidines are key components in the genetic code of living organisms and the pyrimidine scaffold is also found in many bioactive and medicinal compounds. The acidities of these compounds, as represented by their pKas, are of special interest since they determine the species that will prevail under different pH conditions. Here, a quantum chemical quantitative structure–activity relationship (QSAR) approach was employed to estimate these acidities. Density-functional theory calculations at the B3LYP/6-31+G(d,p) level and the SM8 aqueous solvent model were employed, and the energy difference ∆EH2O between the parent compound and its dissociation product was used as a variation parameter. Excellent estimates for both the cation → neutral (pKa1, R2 = 0.965) and neutral → anion (pKa2, R2 = 0.962) dissociations were obtained. A commercial package from Advanced Chemical Design also yielded excellent results for these acidities.
Design, Synthesis, Biological Evaluation, and Molecular Modeling of 2-Difluoromethylbenzimidazole Derivatives as Potential PI3Kα Inhibitors
Authors: Wang Xiangcong , Zhang Moxuan , Zhu Ranran , Wu Zhongshan , Wu Fanhong , Wang Zhonghua , Yu Yanyan
Published: January 2022

PI3Kα is one of the potential targets for novel anticancer drugs. In this study, a series of 2-difluoromethylbenzimidazole derivatives were studied based on the combination of molecular modeling techniques 3D-QSAR, molecular docking, and molecular dynamics. The results showed that the best comparative molecular field analysis (CoMFA) model had q2 = 0.797 and r2 = 0.996 and the best comparative molecular similarity indices analysis (CoMSIA) model had q2 = 0.567 and r2 = 0.960. It was indicated that these 3D-QSAR models have good verification and excellent prediction capabilities. The binding mode of the compound 29 and 4YKN was explored using molecular docking and a molecular dynamics simulation. Ultimately, five new PI3Kα inhibitors were designed and screened by these models. Then, two of them (86, 87) were selected to be synthesized and biologically evaluated, with a satisfying result (22.8 nM for 86 and 33.6 nM for 87).
Nutraceutical Content and Genetic Diversity Share a Common Pattern in New Pomegranate Genotypes
Authors: Arlotta Carmen , Toscano Valeria , Genovese Claudia , Calderaro Pietro , Puglia Giuseppe Diego , Raccuia Salvatore Antonino
Published: January 2022

The nutraceutical value of pomegranate in the treatment of many diseases is well-documented and is linked to its richness in phenolic compounds. This study aims to evaluate the nutraceutical and genetic diversity of novel pomegranate genotypes (G1–G5) in comparison to leading commercial pomegranate varieties, i.e., ‘Wonderful’, ‘Primosole’, ‘Dente di Cavallo’ and ‘Valenciana’. Morphometric measurements were carried out on fruits, accompanied by chemical characterization (total phenolic content, antioxidant activity, carbohydrates and minerals) and the development of four new polymorphic SSR markers involved in the flavonoid pathway. The cultivars displayed a marked variability in the weight and shape of the fruits, as well as in the weight of the arils and juice yield. The highest level of total phenolic content and antioxidant activity was found in ‘Wonderful’ and G4, while the lowest was in ‘Dente di Cavallo’. Furthermore, the results showed that pomegranate juice is an excellent source of minerals, especially potassium, which plays a key role in organ functioning. The new flavonoid-related markers effectively differentiated the cultivars with the same diversity pattern as morpho-chemical characterization, so the SSRs developed in the present study can be used as a rapid tool for the identification of pomegranate cultivars with relevant nutraceutical traits, such as the new genotypes investigated.
Oil Phase Solubility Rather Than Diffusivity Determines the Release of Entrapped Amino Acids and Di-Peptides from Water-in-Oil-in-Water Emulsions
Authors: Kocaman Esra , Rabiti Davide , Murillo Moreno Juan Sebastian , Can Karaca Asli , Van der Meeren Paul
Published: January 2022

The permeation of amino acids and di-peptides with different hydrophobicities across the oil phase in W/O/W double emulsions was investigated at different concentrations, considering the pH of the aqueous phase. Moreover, the particle size, yield of entrapped water and release kinetics of the double emulsions was evaluated as a function of time. Regarding the release of the entrapped amino acids and di-peptides, their hydrophobicity and the pH had a significant effect, whereas the concentration of the dissolved compound did not lead to different release kinetics. The release of the amino acids and di-peptides was faster at neutral pH as compared to acidic pH values due to the increased solute solubility in the oil phase for more hydrophobic molecules at neutral pH. Regarding the effect of the type of oil, much faster amino acid transport was observed through MCT oil as compared to LCT oil, which might be due to its higher solubility and/or higher diffusivity. As di-peptides released faster than amino acids, it follows that the increased solubility overruled the effect from the decreased diffusion coefficient of the dissolved compound in the oil phase.
Bioactive β-Carbolines Harman and Norharman in Sesame Seed Oils in China
Authors: Liu Wei , Yang Zhaoyu , Shi Lili , Li Yun
Published: January 2022

The β-carbolines in our diet, mainly including harman and norharman, are a group of biologically active, naturally occurring plant-derived alkaloids. Fragrant sesame seed oil is one of the most popular flavor edible oils in China. Considering that sesame seeds are roasted at 200–240 °C during the processing of flavor sesame seed oils, it is meaningful to investigate the levels of β-carboline compounds in various sesame seed oils. In this work, the levels of β-carbolines (harman and norharman) in different types of sesame seed oils in China (e.g., pressed fragrant sesame oil, ground fragrant sesame oil) have been determined systematically. The results showed that the levels of total β-carbolines in pressed fragrant sesame oils (700.5~2423.2 μg/kg) were higher than that in ground fragrant sesame oils (660.4~1171.7 μg/kg). Roasting sesame seeds at high temperatures (200–240 °C) led to higher levels of β-carbolines (660~2400 μg/kg) in fragrant sesame seed oils. In addition, the loss of tryptophan might be attributed to the formation of β-carbolines in sesame seeds during the roasting process. In general, fragrant sesame seed oils (pressed fragrant sesame oils, ground fragrant sesame oils) contain higher levels of β-carbolines due to the formation of harman and norharman during the roasting sesame seed process.
Synthesis and Biological Activity of 3-(Heteroaryl)quinolin-2(1H)-ones Bis-Heterocycles as Potential Inhibitors of the Protein Folding Machinery Hsp90
Authors: Larghi Enrique L. , Bruneau Alexandre , Sauvage Félix , Alami Mouad , Vergnaud-Gauduchon Juliette , Messaoudi Samir
Published: January 2022

In the context of our SAR study concerning 6BrCaQ analogues as C-terminal Hsp90 inhibitors, we designed and synthesized a novel series of 3-(heteroaryl)quinolin-2(1H), of types 3, 4, and 5, as a novel class of analogues. A Pd-catalyzed Liebeskind–Srogl cross-coupling was developed as a convenient approach for easy access to complex purine architectures. This series of analogues showed a promising biological effect against MDA-MB231 and PC-3 cancer cell lines. This study led to the identification of the best compounds, 3b (IC50 = 28 µM) and 4e, which induce a significant decrease of CDK-1 client protein and stabilize the levels of Hsp90 and Hsp70 without triggering the HSR response.
Tunning CO2 Separation Performance of Ionic Liquids through Asymmetric Anions
Authors: Soares Bruna F. , Nosov Daniil R. , Pires José M. , Tyutyunov Andrey A. , Lozinskaya Elena I. , Antonov Dmitrii Y. , Shaplov Alexander S. , Marrucho Isabel M.
Published: January 2022

This work aims to explore the gas permeation performance of two newly-designed ionic liquids, [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2], in supported ionic liquid membranes (SILM) configuration, as another effort to provide an overall insight on the gas permeation performance of functionalized-ionic liquids with the [C2mim]+ cation. [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2] single gas separation performance towards CO2, N2, and CH4 at T = 293 K and T = 308 K were measured using the time-lag method. Assessing the CO2 permeation results, [C2mim][CF3BF3] showed an undermined value of 710 Barrer at 293.15 K and 1 bar of feed pressure when compared to [C2mim][BF4], whereas for the [C2mim][CF3SO2C(CN)2] IL an unexpected CO2 permeability of 1095 Barrer was attained at the same experimental conditions, overcoming the results for the remaining ILs used for comparison. The prepared membranes exhibited diverse permselectivities, varying from 16.9 to 22.2 for CO2/CH4 and 37.0 to 44.4 for CO2/N2 gas pairs. The thermophysical properties of the [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2] ILs were also determined in the range of T = 293.15 K up to T = 353.15 K at atmospheric pressure and compared with those for other ILs with the same cation and anion’s with similar chemical moieties.