bluuebunny/crossref_metadata_2025 huggingface dataset:
Enhance ZnO Photocatalytic Performance via Radiation Modified g-C3N4
Authors: Wang Yayang , Yang Xiaojie , Lou Jiahui , Huang Yaqiong , Peng Jian , Li Yuesheng , Liu Yi
Published: December 2022

Environmental pollution, especially water pollution, is becoming increasingly serious. Organic dyes are one type of the harmful pollutants that pollute groundwater and destroy ecosystems. In this work, a series of graphitic carbon nitride (g-C3N4)/ZnO photocatalysts were facilely synthesized through a grinding method using ZnO nanoparticles and g-C3N4 as the starting materials. According to the results, the photocatalytic performance of 10 wt.% CN-200/Z-500 (CN-200, which g-C3N4 was 200 kGy, referred to the irradiation metering. Z-500, which ZnO was 500 °C, referred to the calcination temperature) with the CN-200 exposed to electron beam radiation was better than those of either Z-500 or CN-200 alone. This material displayed a 98.9% degradation rate of MB (20 mg/L) in 120 min. The improvement of the photocatalytic performance of the 10 wt.% CN-200/Z-500 composite material was caused by the improvement of the separation efficiency of photoinduced electron–hole pairs, which was, in turn, due to the formation of heterojunctions between CN-200 and Z-500 interfaces. Thus, this study proposes the application of electron-beam irradiation technology for the modification of photocatalytic materials and the improvement of photocatalytic performance.
Nearest-Neighbour and Non-Nearest-Neighbour Non-Covalent Interactions between Substituents in the Aromatic Systems: Experimental and Theoretical Investigation of Functionally Substituted Benzophenones
Authors: Samarov Artemiy A. , Kondratev Stanislav O. , Verevkin Sergey P.
Published: December 2022

Benzophenone derivatives exhibit not only biological activity but also act as photo initiator and UV blocker. We carried out experimental and theoretical thermochemical studies of hydroxy- and methoxy-substituted benzophenones. Standard molar enthalpies of vaporisation were obtained from the temperature dependence of vapour pressures measured by the transpiration method. The thermodynamic data on phase transitions available in the literature (crystal–gas, crystal–liquid, and liquid–gas) were also collected and evaluated. High-level quantum chemical methods G3MP2 and G4 were used to estimate the standard molar enthalpies of formation of substituted benzophenones in the gas phase and establish agreement between experimental and theoretical results. The application of the “centrepiece” group-contribution approach to hydroxy- and methoxy-substituted benzophenones was demonstrated. A quantitative assessment of the hydrogen bond was carried out using various approaches based on experimental data and quantum chemical calculations.
Recombinant Spider Silk Fiber with High Dimensional Stability in Water and Its NMR Characterization
Authors: Asakura Tetsuo , Matsuda Hironori , Naito Akira , Okamura Hideyasu , Suzuki Yu , Abe Yunosuke
Published: December 2022

Spider dragline silk has unique characteristics of strength and extensibility, including supercontraction. When we use it as a biomaterial or material for textiles, it is important to suppress the effect of water on the fiber by as much as possible in order to maintain dimensional stability. In order to produce spider silk with a highly hydrophobic character, based on the sequence of ADF-3 silk, we produced recombinant silk (RSSP(VLI)) where all QQ sequences were replaced by VL, while single Q was replaced by I. The artificial RSSP(VLI) fiber was prepared using formic acid as the spinning solvent and methanol as the coagulant solvent. The dimensional stability and water absorption experiments of the fiber were performed for eight kinds of silk fiber. RSSP(VLI) fiber showed high dimensional stability, which is suitable for textiles. A remarkable decrease in the motion of the fiber in water was made evident by 13C solid-state NMR. This study using 13C solid-state NMR is the first trial to put spider silk to practical use and provide information regarding the molecular design of new recombinant spider silk materials with high dimensional stability in water, allowing recombinant spider silk proteins to be used in next-generation biomaterials and materials for textiles.
Recent Advances in DMSO-Based Direct Synthesis of Heterocycles
Authors: Cui Hai-Lei
Published: December 2022

Besides serving as a low-toxicity, inexpensive and easily accessible solvent, dimethyl sulfoxide (DMSO) has also been extensively used as a versatile reagent for the synthesis of functionalized molecules. Dimethyl sulfoxide can not only be utilized as a carbon source, a sulfur source and an oxygen source, but also be employed as a crucial oxidant enabling various transformations. The past decade has witnessed a large number of impressive achievements on the direct synthesis of heterocycles as well as modifications of heterocyclic compounds by applying DMSO as a reagent. This review summarized the DMSO-based direct heterocycle constructions from 2012 to 2022.
Synthesis and Anti-Inflammatory Activity of 1-Methylhydantoin Cinnamoyl Imides
Authors: Wang Shihan , Ji Li , Zhang Dongxue , Guo Hongye , Wang Yongsheng , Li Wei
Published: December 2022

In this study, 1-methylhydantoin cinnamic imides were synthesized from 1-methylhydantoin and trans-cinnamic acid, and their anti-inflammatory activity was investigated. The anti-inflammatory activity in vitro was evaluated by measuring the contents of NO, TNF-α and IL-1β in the supernatant of RAW264.7 cells stimulated by LPS. The cytotoxicity of 1-methylhydantoin cinnamoyl imides on RAW264.7 cells was detected using the CCK-8 method. The results showed that compounds 2 and 4 can significantly inhibit the release of NO and reduce the secretion of TNF-α and IL-1β. Compound 3 inhibited the production of TNF-α. The inhibition rate of COX was evaluated in vitro. The in vivo anti-inflammatory activities of the five compounds were evaluated by establishing an animal model of xylene ear swelling. The results showed that 1-methylhydantoin cinnamic imides could alleviate xylene-induced ear edema in mice in a dose-dependent manner. Among them, the effect of compound 5 was the most significant. Under the action of high dosage, its ear swelling inhibition rate was as high as 52.08%.
One-Dimensional Iodoantimonate(III) and Iodobismuthate(III) Supramolecular Hybrids with Diiodine: Structural Features, Stability and Optical Properties
Authors: Korobeynikov Nikita A. , Usoltsev Andrey N. , Abramov Pavel A. , Sokolov Maxim N. , Adonin Sergey A.
Published: December 2022

Two isostructural pairs of supramolecular iodoantimonate(III) and iodobismuthate(III) complexes with I2 units “trapped” in solid state via halogen bonding—Cat3[[M2I9](I2)} (Cat = tetramethylammonium and 1-methylpyridinium, M = Sb(III) and Bi(III)) were prepared. For all compounds, values of optical band gaps were determined, together with thermal stability; the complexes were additionally characterized by Raman spectroscopy.
A Comprehensive HPTLC-Based Analysis of the Impacts of Temperature on the Chemical Properties and Antioxidant Activity of Honey
Authors: Islam Md Khairul , Sostaric Tomislav , Lim Lee Yong , Hammer Katherine , Locher Cornelia
Published: December 2022

Honeys are commonly subjected to a series of post-harvest processing steps, such as filtration and/or radiation treatment and heating to various temperatures, which might affect their physicochemical properties and bioactivity levels. Therefore, there is a need for robust quality control assessments after honey processing and storage to ensure that the exposure to higher temperatures, for example, does not compromise the honey’s chemical composition and/or antioxidant activity. This paper describes a comprehensive short-term (48 h) and long-term (5 months) study of the effects of temperature (40 °C, 60 °C and 80 °C) on three commercial honeys (Manuka, Marri and Coastal Peppermint) and an artificial honey, using high-performance thin-layer chromatography (HPTLC) analysis. Samples were collected at baseline, at 6 h, 12 h, 24 h and 48 h, and then monthly for five months. Then, they were analysed for potential changes in their organic extract HPTLC fingerprints, in their HPTLC-DPPH total band activities, in their major sugar composition and in their hydroxymethylfurfural (HMF) content. It was found that, while all the assessed parameters changed over the monitoring period, changes were moderate at 40 °C but increased significantly with increasing temperature, especially the honeys’ HPTLC-DPPH total band activity and HMF content.
Synthesis, Photochromic and Luminescent Properties of Ammonium Salts of Spiropyrans
Authors: Khuzin Artur A. , Galimov Dim I. , Tulyabaev Artur R. , Khuzina Liliya L.
Published: December 2022

New salts of photochromic indoline spiropyrans capable of reversibly responding to UV radiation were synthesized to develop light-controlled materials. Photoinduced reactions of the synthesized compounds were studied using absorption and luminescence spectroscopies, and the quantum yields of photoisomerization and other spectral and kinetic characteristics were measured. It was shown that the light sensitivity and photostability of the synthesized compounds are considerably influenced by the length of the spacer between the indole and ammonium nitrogen atoms.
Fabrication and Characterization of Konjac Glucomannan/Oat β-Glucan Composite Hydrogel: Microstructure, Physicochemical Properties and Gelation Mechanism Studies
Authors: Geng Xiaoyuan , Zhao Nuo , Song Xiwang , Wu Jianfu , Zhu Qiaomei , Wu Tao , Chen Haixia , Zhang Min
Published: December 2022

The aim of this study was to evaluate the effect of oat β-glucan on the formation mechanism, microstructure and physicochemical properties of konjac glucomannan (KGM) composite hydrogel. The dynamic rheology results suggested that the addition of oat β-glucan increased the viscoelastic modulus of the composite hydrogel, which was conducive to the formation of a stronger gel network. Gelling force experiments showed that hydrogen bonds and hydrophobic interactions participated in the formation of the gel network. Textural profile analysis results found that the amount of oat β-glucan was positively correlated with the elasticity, cohesiveness and chewiness of the composite hydrogel. The water-holding capacity of the composite hydrogel was enhanced significantly after the addition of oat β-glucan (p < 0.05), which was 18.3 times that of the KGM gel. The thermal stability of KGM gel was enhanced after the addition of oat β-glucan with the increase in Tmax being approximately 30 °C. Consequently, a composite hydrogel based on KGM and oat β-glucan was a strategy to overcome pure KGM gel shortcomings.
Enhancement of Antioxidant Property of N-Carboxymethyl Chitosan and Its Application in Strawberry Preservation
Authors: Bian Luyao , Sun Huigang , Zhou Ying , Tao Yang , Zhang Chong
Published: December 2022

Bio-enzymatic grafting phenolic acid to chitosan derivative is an efficient and environmentally friendly molecular synthesis technology. In the present study, N-carboxymethyl chitosan (CMCS) was grafted with gallic acid (GA) using recombinant bacterial laccase from Streptomyces coelicolor as a catalyst. GA and CMCS were successfully grafted as determined by measuring amino acid content, Fourier transform infrared (FTIR) spectroscopy and ultraviolet-visible (UV-Vis) spectroscopy. Then, the effect of GA-g-CMCS coating on the freshness of strawberries at 20 ± 2 °C was explored. The physiological and biochemical quality indicators of strawberries during storage were monitored. The 1.5% GA-g-CMCS coating helped to protect the antioxidant properties and nutrients of strawberries and extend the shelf life. Specifically, it reduced the weight loss of strawberries during preservation (originally 12.7%) to 8.4%, maintained titratable acidity content (TA) residuals above 60% and reduced decay rate from 36.7% to 8.9%. As a bioactive compound, GA-g-CMCS has the potential to become an emerging food packing method. These results provide a theoretical basis and reference method for the subsequent synthesis and application of CMCS derivatives.
Research Progress in Fluorescent Probes for Arsenic Species
Authors: Qiu Yunliang , Yu Shuaibing , Li Lianzhi
Published: December 2022

Arsenic is a toxic non-metallic element that is widely found in nature. In addition, arsenic and arsenic compounds are included in the list of Group I carcinogens and toxic water pollutants. Therefore, rapid and efficient methods for detecting arsenic are necessary. In the past decade, a variety of small molecule fluorescent probes have been developed, which has been widely recognized for their rapidness, efficiency, convenience and sensitivity. With the development of new nanomaterials (AuNPs, CDs and QDs), organic molecules and biomolecules, the conventional detection of arsenic species based on fluorescence spectroscopy is gradually transforming from the laboratory to the portable kit. Therefore, in view of the current research status, this review introduces the research progress of both traditional and newly developed fluorescence spectrometry based on novel materials for arsenic detection, and discusses the potential of this technology in the rapid screening and field testing of water samples contaminated with arsenic. The review also discusses the problems that still exist in this field, as well as the expectations.
Hybrid Silsesquioxane/Benzoate Cu7-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity
Authors: Bilyachenko Alexey N. , Khrustalev Victor N. , Gutsul Evgenii I. , Zueva Anna Y. , Korlyukov Alexander A. , Shul’pina Lidia S. , Ikonnikov Nikolay S. , Dorovatovskii Pavel V. , Gelman Dmitri , Shubina Elena S. , Shul’pin Georgiy B.
Published: December 2022

A series of phenylsilsesquioxane-benzoate heptacopper complexes 1–3 were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure 1. A unique multi-ligation of copper ions (from (i) silsesquioxane, (ii) benzoate, (iii) benzyl alcohol, (iv) pyridine, (v) dimethyl-formamide and (vi) water ligands) was found in 1. Directed self-assembly using benzoic acid as a reactant afforded complexes 2–3 with the same main structural features as for 1, namely heptanuclear core coordinated by (i) two distorted pentameric cyclic silsesquioxane and (ii) four benzoate ligands, but featuring other solvate surroundings. Complex 3 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 °C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of n-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex 3 exhibits a high activity in the oxidation of alcohols.
Multicolor Emissive Phosphorescent Iridium(III) Complexes Containing L-Alanine Ligands: Photophysical and Electrochemical Properties, DFT Calculations, and Selective Recognition of Cu(II) Ions
Authors: Chu Xi , Huang Yichuan , Li Wenhao , Zhao Shisheng , Li Hongyan , Lu Aidang
Published: December 2022

Three novel Ir(III) complexes, (ppy)2Ir(L-alanine) (Ir1) (ppy = 2-phenylpyridine), (F4ppy)2Ir(L-alanine) (Ir2) (F4ppy = 2-(4-fluorophenyl)pyridine), and (F2,4,5ppy)2Ir(L-alanine) (Ir3) (F2,4,5ppy = 2-(2,4,5-trifluorophenyl)pyridine), based on simple L-alanine as ancillary ligands were synthesized and investigated. Due to the introduction of fluorine substituents on the cyclometalated ligands, complexes Ir1–Ir3 exhibited yellow to sky-blue emissions (λem = 464–509 nm) in acetonitrile solution. The photoluminescence quantum yields (PLQYs) of Ir1–Ir3 ranged from 0.48–0.69, of which Ir3 with sky-blue luminescence had the highest PLQY of 0.69. The electrochemical study and density functional theory (DFT) calculations show that the highest occupied molecular orbital (HOMOs) energy of Ir1–Ir3 are stabilized by the introduction of fluorine substituents on the cyclometalated ligands, while L-alanine ancillary ligand has little contribution to HOMOs and lowest unoccupied molecular orbitals (LUMOs). Moreover, Ir1–Ir3 presented an excellent response to Cu2+ with a high selectivity, strong anti-interference ability, and short response time. Such a detection was based on significant phosphorescence quenching of their emissions, showing the potential application in chemosensors for Cu2+.
Recovery of Naringin-Rich Flavonoid Extracts from Agroresidues with Anxiolytic- and Antidepressant-like Effects in Mice
Authors: Hernández-Vázquez Liliana , Cassani Julia , Heyerdahl-Viau Ivo , Martínez-Casares Rubria M. , Luna Héctor , Dorantes-Barrón Ana María , Arrieta-Báez Daniel , Estrada-Reyes Rosa
Published: December 2022

Citrus paradisi species belong to the Rutaceae family, and it is commonly known as grapefruit. Grapefruit consumption involves a large amount of waste that goes to landfills and produces significant pollution affecting the human health. To examine this phenomenon, we designed an efficient chemical method that recovers naringin-rich flavonoid extracts from the fresh waste of grapefruits, by using the solvent impregnation resin method (SIR) with XAD-4 amberlite and either methanol or water as elution systems. Additionally, we focused on evaluating these extracts’ anxiolytic- and antidepressant-like effects in behavioral predictive paradigms in mice. According to direct Principal Component Analysis (PCA) by NMR, and Direct Injection Electrospray Ionization-Mass Spectrometry (DIESI-MS), methanol extracts obtained after resin treatment were free of coumarin compounds and evinced had a high content of naringin. Poncirin, phenylalanine, chrysin 5,7-dimethyl ether, 5,7-dimethoxy-4′-hydroxyflavanone, 2,3-dihydro-2-(4-hydroxyphenyl)-5,6,7,8-tetramethoxy-4H-1-benzopyran-4-one, tetrahydrocurcumin, corchoionoside C, 6′-coumaroyl-1′-O-[2-(3,4-dihydroxyphenyl) ethyl]-β-D-glucopyranoside were also detected. Naringin-rich methanol extract caused a clear anxiolytic-like effect in the Elevated Plus Maze (EPM) and the Hole-Board (HBT) Tests, increasing oral doses of this extract did not produce a sedative effect. A single oral dose caused an antidepressant-like effect in the Tail Suspension Test (TST), while repeated administrations of the methanol extract elicited a robust antidepressant effect in the Forced Swimming Test (FST) in mice. Our evidence highlights the importance of bioprospecting studies of organic waste with therapeutic potentials, such as anxiety and depression disorders.
Optimization of Wall Material of Freeze-Dried High-Bioactive Microcapsules with Yellow Onion Rejects Using Simplex Centroid Mixture Design Approach Based on Whey Protein Isolate, Pectin, and Sodium Caseinate as Incorporated Variables
Authors: Azarpazhooh Elham , Sharayei Parvin , Rui Xin , Gharibi-Tehrani Mehranoosh , Ramaswamy Hosahalli S.
Published: December 2022

For the food sector, onion rejects are an appealing source of value-added byproducts. Bioactive compounds were recovered from yellow onion rejects using a pulse electric field process at 6000 v and 60 pulses. The onion extract was encapsulated with whey protein isolate (WPI), pectin (P), and sodium caseinate (SC) with a mass ratio of 1:5 (extract/wall material, w/w). A Simplex lattice with augmented axial points in the mixture design was applied for the optimization of wall material for the encapsulation of onion reject extract by freeze-drying (FD). The optimal wall materials were 47.6 g/100 g (SC), 10.0 g/100 g (P), and 42.4 g/100 g (WPI), with encapsulation yield (EY) of 85.1%, total phenolic content (TPC) of 48.7 mg gallic acid equivalent/g DW, total flavonoid content (TFC) of 92.0 mg quercetin equivalent/g DW, and DPPH capacity of 76.1%, respectively. The morphological properties of the optimal encapsulate demonstrated spherical particles with a rough surface. At optimal conditions, the minimum inhibitory concentration (MIC) of the extract (mean diameter of inhibition zone: 18.8 mm) was shown as antifungal activity against Aspergillus niger.
HPLC, FTIR and GC-MS Analyses of Thymus vulgaris Phytochemicals Executing In Vitro and In Vivo Biological Activities and Effects on COX-1, COX-2 and Gastric Cancer Genes Computationally
Authors: Saleem Ayesha , Afzal Muhammad , Naveed Muhammad , Makhdoom Syeda Izma , Mazhar Modasrah , Aziz Tariq , Khan Ayaz Ali , Kamal Zul , Shahzad Muhammad , Alharbi Metab , Alshammari Abdulrahman
Published: December 2022

Medicinal plants have played an essential role in the treatment of various diseases. Thymus vulgaris, a medicinal plant, has been extensively used for biological and pharmaceutical potential. The current study was performed to check the biopotential of active biological compounds. The GC-MS analysis identified 31 compounds in methanolic crude extract, among which thymol, carvacrol, p-cymene, and eugenol are the main phytoconstituents present in T. vulgaris. The HPLC analysis quantified that flavonoids and phenolic acids are present in a good concentration in the active fraction of ethyl acetate and n-butanol. FTIR confirmed the presence of functional groups such as phenols, a carboxylic group, hydroxy group, alcohols, and a benzene ring. Among both fractions, ethyl acetate showed high antioxidant activity in the DPPH (84.1 0.88) and ABTS (87.1 0.89) assays, respectively. The anti-inflammatory activity of the fractions was done in vitro and in vivo by using a carrageenan-induced paw edema assay, while the hexane-based extract showed high anti-inflammatory activity (57.1 0.54) in a dose-response manner. Furthermore, the lead compound responsible for inhibition in the denaturation of proteins is thymol, which exhibits the highest binding affinity with COX1 (−6.4 KJ/mol) and COX2 (−6.3 KJ/mol) inflammatory proteins. The hepatotoxicity analysis showed that plant-based phytoconstituents are safe to use and have no toxicity, with no necrosis, fibrosis, and vacuolar degeneration, even at a high concentration of 800 mg/kg body weight. Furthermore, the in silico analysis of HPLC phytochemical compounds against gastric cancer genes showed that chlorogenic acid exhibited anticancer activity and showed good drug-designing characteristics. Thrombolysis and hemolysis are the major concerns of individuals suffering from gastric cancer. However, the T. vulgaris fractions showed thrombolysis from 17.6 to 5.4%; similarly, hemolysis ranged from 9.73 to 7.1% at a concentration of 12 mg/mL. The phytoconstituents present in T. vulgaris have the potential for multiple pharmacological applications. This should be further investigated to isolate bioactive compounds that can be used for the treatment of different ailments.
Chemical Composition of Tobacco Seed Oils and Their Antioxidant, Anti-Inflammatory, and Whitening Activities
Authors: Gu Ji , Zhang Xiaoyu , Song Biqing , Zhou Dongjie , Niu Yongzhi , Cheng Guiguang , Zheng Yunye , Wang Yudan
Published: December 2022

Tobacco seeds are a valuable food oil resource, and tobacco seed oil is rich in nutrients, especially polyunsaturated fatty acids. The aim of this work was to perform a comprehensive study on the chemical constituents, and the antioxidant, anti-inflammatory, and whitening activities of tobacco seed oils (NC89 and BS4). A GC/MS analysis revealed that NC89 and BS4 had 11 and 6 volatile compounds, respectively. The PUFA contents in NC89 and BS4 were 74.98% and 72.84%, respectively. These two tobacco seed oils also presented good radical scavenging capacities with the neutralization of ABTS, OH−, and superoxide (O2−) radicals in a concentration-dependent manner. Meanwhile, NC89 and BS4 inhibited reactive oxygen species (ROS) accumulation and cell apoptosis, enhanced SOD and CAT activities, and increased the GSH content in H2O2-induced HepG2 cells. In addition, NC89 and BS4 exhibited significant anti-inflammatory activities by inhibiting the expressions of NO, TNF-α, IL-1β, and IL-6 in LPS-induced RAW.264.7 cells through the regulation of the MAPK signaling pathway. Moreover, NC89 and BS4 expressed whitening activities by inhibiting tyrosinase activity and intracellular melanin production. Therefore, tobacco seed oils could be used as an important oil resource for the development of high value-added products.
Advances in Atroposelectively De Novo Synthesis of Axially Chiral Heterobiaryl Scaffolds
Authors: Zhang Xiaoke , Liu Ya-Zhou , Shao Huawu , Ma Xiaofeng
Published: December 2022

Axially chiral heterobiaryl frameworks are privileged structures in many natural products, pharmaceutically active molecules, and chiral ligands. Therefore, a variety of approaches for constructing these skeletons have been developed. Among them, de novo synthesis, due to its highly convergent and superior atom economy, serves as a promising strategy to access these challenging scaffolds including C-N, C-C, and N-N chiral axes. So far, several elegant reviews on the synthesis of axially chiral heterobiaryl skeletons have been disclosed, however, atroposelective construction of the heterobiaryl subunits by de novo synthesis was rarely covered. Herein, we summarized the recent advances in the catalytic asymmetric synthesis of the axially chiral heterobiaryl scaffold via de novo synthetic strategies. The related mechanism, scope, and applications were also included.
The Lyotropic Nature of Halates: An Experimental Study
Authors: Acar Mert , Tatini Duccio , Ninham Barry W. , Rossi Federico , Marchettini Nadia , Lo Nostro Pierandrea
Published: December 2022

Unlike halides, where the kosmotropicity decreases from fluoride to iodide, the kosmotropic nature of halates apparently increases from chlorate to iodate, in spite of the lowering in the static ionic polarizability. In this paper, we present an experimental study that confirms the results of previous simulations. The lyotropic nature of aqueous solutions of sodium halates, i.e., NaClO3, NaBrO3, and NaIO3, is investigated through density, conductivity, viscosity, and refractive index measurements as a function of temperature and salt concentration. From the experimental data, we evaluate the activity coefficients and the salt polarizability and assess the anions’ nature in terms of kosmotropicity/chaotropicity. The results clearly indicate that iodate behaves as a kosmotrope, while chlorate is a chaotrope, and bromate shows an intermediate nature. This experimental study confirms that, in the case of halates XO3−, the kosmotropic–chaotropic ranking reverses with respect to halides. We also discuss and revisit the role of the anion’s polarizability in the interpretation of Hofmeister phenomena.
Spectroelectrochemical and Theoretical Study of [Si(ttpy)2](PF6)4: A Potential Polychromatic Electrochromic Dye
Authors: Peloquin Derek M. , Bimukhanov Askhat N. , Aldongarov Anuar A. , Merkert Jon W. , Donovan-Merkert Bernadette T. , Schmedake Thomas A.
Published: December 2022

Complexes consisting of earth-abundant main group metals such as silicon with polypyridine ligands are of interest for a variety of optical and electronic applications including as electrochromic colorants. Previous spectroelectrochemical studies with tris(2,2′-bipyridyl)silicon(IV) hexafluorophosphate, [Si(bpy)3](PF6)4, demonstrated an ability to control the color saturation of the potential electrochromic dye, with the intensity of the dye’s green color increasing as the charge state sequentially reduces from 4+ to 1+. In this study, the synthesis of bis(4′-(4-tolyl)-2,2′:6′,2″-terpyridine)silicon(IV) hexafluorophosphate, [Si(ttpy)2](PF6)4, is reported along with electrochemical and spectroelectrochemical analyses. Computational modeling (density functional theory) is used to further elucidate the electrochromic properties of previously reported Si(bpy)3n+ species and the new Si(ttpy)2n+ species. While the homoleptic tris(bidentate)silicon(IV) complexes are attractive as electrochromic dyes for tunable color saturation, the bis(tridentate)silicon(IV) complexes are attractive as polychromatic electrochromic dyes.
Magnetic Polyethyleneimine Nanoparticles Fabricated via Ionic Liquid as Bridging Agents for Laccase Immobilization and Its Application in Phenolic Pollutants Removal
Authors: Liu Runtang , Zhang Wei , Wang Shushu , Xu Huajin , Hu Yi
Published: December 2022

In this study, polyethyleneimine was combined with magnetic Fe3O4 nanoparticles through the bridging of carboxyl-functionalized ionic liquid, and laccase was loaded onto the carrier by Cu2+ chelation to achieve laccase immobilization (MCIL–PEI–Cu–lac). The carrier was characterized by Fourier transform infrared spectroscopy, scanning electron microscope, thermogravimetric analysis, X-ray diffraction analysis, magnetic hysteresis loop and so on. MCIL–PEI–Cu–lac has good immobilization ability; its loading and activity retention could reach 52.19 mg/g and 91.65%, respectively. Compared with free laccase, its thermal stability and storage stability have been significantly improved, as well. After 6 h of storage at 60 °C, 51.45% of the laccase activity could still be retained, and 81.13% of the laccase activity remained after 1 month of storage at 3 °C. In the pollutants removal test, the removal rate of 2,4-dichlorophenol (10 mg/L) by MCIL–PEI–Cu–lac could reach 100% within 10 h, and the removal efficiency could still be maintained 60.21% after repeated use for 8 times. In addition, MCIL–PEI–Cu–lac also has a good removal effect on other phenolic pollutants (such as bisphenol A, phenol, 4-chlorophenol, etc.). Research results indicated that an efficient strategy for laccase immobilization to biodegrade phenolic pollutants was developed.
Abnormalities of the Halogen Bonds in the Complexes between Y2CTe (Y = H, F, CH3) and XF (X = F, Cl, Br, I)
Authors: Wang Ya-Qian , Wang Rui-Jing , Li Qing-Zhong , Yu Zhi-Wu
Published: December 2022

In this work, the hydrogen bonds and halogen bonds in the complexes between Y2CTe (Y = H, F, CH3) and XF (X = F, Cl, Br, I) have been studied by quantum chemical calculations. We found three interesting abnormalities regarding the interactions. Firstly, the strength of halogen bonds increases in the order of IF < BrF < ClF < F2. Secondly, the halogen bonds formed by F2 are very strong, with an interaction energy in the range between −199.8 and −233.1 kJ/mol. Thirdly, all the halogen bonds are stronger than the hydrogen bonds in the systems we examined. All these results are against the general understanding of halogen bonds. These apparent abnormal properties are reconciled with the high polarizability of the Te atom and the strong inducing effect of F on the Te atom of Y2CTe. These findings provide a new perspective on halogen bonds. Additionally, we also proposed bonding distance-based methods to compare the strength of halogen/hydrogen bonds formed between different donor atoms and the same acceptor atom.
All-Polymer Piezo-Composites for Scalable Energy Harvesting and Sensing Devices
Authors: Stiubianu George-Theodor , Bele Adrian , Bargan Alexandra , Potolinca Violeta Otilia , Asandulesa Mihai , Tugui Codrin , Tiron Vasile , Hamciuc Corneliu , Dascalu Mihaela , Cazacu Maria
Published: December 2022

Silicone elastomer composites with piezoelectric properties, conferred by incorporated polyimide copolymers, with pressure sensors similar to human skin and kinetic energy harvester capabilities, were developed as thin film (<100 micron thick) layered architecture. They are based on polymer materials which can be produced in industrial amounts and are scalable for large areas (m2). The piezoelectric properties of the tested materials were determined using a dynamic mode of piezoelectric force microscopy. These composite materials bring together polydimethylsiloxane polymers with customized poly(siloxane-imide) copolymers (2–20 wt% relative to siloxanes), with siloxane segments inserted into the structure to ensure the compatibility of the components. The morphology of the materials as free-standing films was studied by SEM and AFM, revealing separated phases for higher polyimide concentration (10, 20 wt%). The composites show dielectric behavior with a low loss (<10−1) and a relative permittivity superior (3–4) to pure siloxane within a 0.1–106 Hz range. The composite in the form of a thin film can generate up to 750 mV under contact with a 30 g steel ball dropped from 10 cm high. This capability to convert a pressure signal into a direct current for the tested device has potential for applications in self-powered sensors and kinetic energy-harvesting applications. Furthermore, the materials preserve the known electromechanical properties of pure polysiloxane, with lateral strain actuation values of up to 6.2% at 28.9 V/μm.
Essential Oils Encapsulated in Zeolite Structures as Delivery Systems (EODS): An Overview
Authors: Ferreira Alexandra P. , Almeida-Aguiar Cristina , Costa Susana P. G. , Neves Isabel C.
Published: December 2022

Essential oils (EO) obtained from plants have proven industrial applications in the manufacturing of perfumes and cosmetics, in the production and flavoring of foods and beverages, as therapeutic agents in aromatherapy, and as the active principles or excipients of medicines and pharmaceutics due to their olfactory, physical-chemical, and biological characteristics. On behalf of the new paradigm of a more natural and sustainable lifestyle, EO are rather appealing due to their physical, chemical, and physiological actions in human beings. However, EO are unstable and susceptible to degradation or loss. To tackle this aspect, the encapsulation of EO in microporous structures as zeolites is an attractive solution, since these host materials are cheap and non-toxic to biological environments. This overview provides basic information regarding essential oils, including their recognized benefits and functional properties. Current progress regarding EO encapsulation in zeolite structures is also discussed, highlighting some representative examples of essential oil delivery systems (EODS) based on zeolites for healthcare applications or aromatherapy.
HPLC Enantioseparation of Rigid Chiral Probes with Central, Axial, Helical, and Planar Stereogenicity on an Amylose (3,5-Dimethylphenylcarbamate) Chiral Stationary Phase
Authors: Rizzo Simona , Benincori Tiziana , Fontana Francesca , Pasini Dario , Cirilli Roberto
Published: December 2022

The chiral resolving ability of the commercially available amylose (3,5-dimethylphenylcarbamate)-based chiral stationary phase (CSP) toward four chiral probes representative of four kinds of stereogenicity (central, axial, helical, and planar) was investigated. Besides chirality, the evident structural feature of selectands is an extremely limited conformational freedom. The chiral rigid analytes were analyzed by using pure short alcohols as mobile phases at different column temperatures. The enantioselectivity was found to be suitable for all compounds investigated. This evidence confirms that the use of the amylose-based CSP in HPLC is an effective strategy for obtaining the resolution of chiral compounds containing any kind of stereogenic element. In addition, the experimental retention and enantioselectivity behavior, as well as the established enantiomer elution order of the investigated chiral analytes, may be used as key information to track essential details on the enantiorecognition mechanism of the amylose-based chiral stationary phase.
Glycan-Based Electrochemical Biosensors: Promising Tools for the Detection of Infectious Diseases and Cancer Biomarkers
Authors: Echeverri Danilo , Orozco Jahir
Published: December 2022

Glycan-based electrochemical biosensors are emerging as analytical tools for determining multiple molecular targets relevant to diagnosing infectious diseases and detecting cancer biomarkers. These biosensors allow for the detection of target analytes at ultra-low concentrations, which is mandatory for early disease diagnosis. Nanostructure-decorated platforms have been demonstrated to enhance the analytical performance of electrochemical biosensors. In addition, glycans anchored to electrode platforms as bioreceptors exhibit high specificity toward biomarker detection. Both attributes offer a synergy that allows ultrasensitive detection of molecular targets of clinical interest. In this context, we review recent advances in electrochemical glycobiosensors for detecting infectious diseases and cancer biomarkers focused on colorectal cancer. We also describe general aspects of structural glycobiology, definitions, and classification of electrochemical biosensors and discuss relevant works on electrochemical glycobiosensors in the last ten years. Finally, we summarize the advances in electrochemical glycobiosensors and comment on some challenges and limitations needed to advance toward real clinical applications of these devices.
Photocatalytic Aerobic Oxidation of Biomass-Derived 5-HMF to DFF over MIL-53(Fe)/g-C3N4 Composite
Authors: Huang Danyao , Wang Hao , Wu Ying
Published: December 2022

A MIL-53(Fe)/g-C3N4 heterogeneous composite was synthesized and applied in photocatalytic oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF). The systematic investigation indicated that the introduction of MIL-53(Fe) into g-C3N4 increased the specific surface area, broadened the visible-light response region, and promoted the separation efficiency of the photo-generated electron-hole pairs. The 10% MIL-53(Fe)/g-C3N4 heterogeneous composite achieved the best photocatalytic oxidation activity with 74.5% of 5-HMF conversion under simulated sunlight, which was much higher than that of pristine g-C3N4 and MIL-53(Fe). The MIL-53(Fe)/g-C3N4 composite displayed good photocatalytic reusability and stability. Based on the characterization results and photocatalytic performance, a Z-scheme photocatalytic mechanism of the MIL-53(Fe)/g-C3N4 composite was suggested, and a possible reaction route was deduced.
The Formation of Inherently Chiral Calix[4]quinolines by Doebner–Miller Reaction of Aldehydes and Aminocalixarenes
Authors: Tlustý Martin , Eigner Václav , Dvořáková Hana , Lhoták Pavel
Published: December 2022

The formation of inherently chiral calix[4]arenes by the intramolecular cyclization approach suffers from a limited number of suitable substrates for these reactions. Here, we report an easy way to prepare one class of such compounds: calixquinolines, which can be obtained by the reaction of aldehydes with easily accessible aminocalix[4]arenes in acidic conditions (Doebner–Miller reaction). The synthetic procedure represents a very straightforward approach to the inherently chiral macrocyclic systems. The complexation studies revealed the ability of these compounds to complex quaternary ammonium salts with different stoichiometries depending on the guest molecules. At the same time, the ability of enantioselective complexation of chiral N-methylammonium salts was demonstrated.
The Chemistry of Phenylimidotechnetium(V) Complexes with Isocyanides: Steric and Electronic Factors
Authors: Claude Guilhem , Zeh Laura , Roca Jungfer Maximilian , Hagenbach Adelheid , Figueroa Joshua S. , Abram Ulrich
Published: December 2022

Organometallic approaches are of ongoing interest for the development of novel functional 99mTc radiopharmaceuticals, while the basic organotechnetium chemistry seems frequently to be little explored. Thus, structural and reactivity studies with the long-lived isotope 99Tc are of permanent interest as the foundation for further progress in the related radiopharmaceutical research with this artificial element. Particularly the knowledge about the organometallic chemistry of high-valent technetium compounds is scarcely developed. Here, phenylimido complexes of technetium(V) with different isocyanides are introduced. They have been synthesized by ligand-exchange procedures starting from [Tc(NPh)Cl3(PPh3)2]. Different reactivity patterns and products have been obtained depending on the steric and electronic properties of the individual ligands. This involves the formation of 1:1 and 1:2 exchange products of Tc(V) with the general formulae [Tc(NPh)Cl3(PPh3)(isocyanide)], cis- or trans-[Tc(NPh)Cl3(isocyanide)2], but also the reduction in the metal and the formation of cationic technetium(I) complex of the formula [Tc(isocyanide)6]+ when p-fluorophenyl isocyanide is used. The products have been studied by single-crystal X-ray diffraction and spectroscopic methods, including IR and multinuclear NMR spectroscopy. DFT calculations on the different isocyanides allow the prediction of their reactivity towards electron-rich and electron-deficient metal centers by means of the empirical SADAP parameter, which has been derived from the potential energy surface of the electron density on their potentially coordinating carbon atoms.
Novel 1,2,3-Triazole-Based Benzothiazole Derivatives: Efficient Synthesis, DFT, Molecular Docking, and ADMET Studies
Authors: Mirjafary Zohreh , Mohammad Karbasi Mahdieh , Hesamzadeh Parsa , Shaker Hamid Reza , Amiri Asghar , Saeidian Hamid
Published: December 2022

A new series of 1,2,3-triazole derivatives 5a–f based on benzothiazole were synthesized by the 1,3-dipolar cycloaddition reaction of S-propargyl mercaptobenzothiazole and α-halo ester/amide in moderate to good yields (47–75%). The structure of all products was characterized by 1H NMR, 13C NMR, and CHN elemental data. This protocol is easy and green and proceeds under mild and green reaction conditions with available starting materials. The structural and electronic analysis and 1H and 13C chemical shifts of the characterized structure of 5e were also calculated by applying the B3LYP/6-31 + G(d, p) level of density functional theory (DFT) method. In the final section, all the synthesized compounds were evaluated for their anti-inflammatory activity by biochemical COX-2 inhibition, antifungal inhibition with CYP51, anti-tuberculosis target protein ENR, DPRE1, pks13, and Thymidylate kinase by molecular docking studies. The ADMET analysis of the molecules 5a–f revealed that 5d and 5a are the most-promising drug-like molecules out of the six synthesized molecules.
Lycopene, Mesoporous Silica Nanoparticles and Their Association: A Possible Alternative against Vulvovaginal Candidiasis?
Authors: Carvalho Gabriela Corrêa , Marena Gabriel Davi , Leonardi Gabriela Ricci , Sábio Rafael Miguel , Corrêa Ione , Chorilli Marlus , Bauab Tais Maria
Published: December 2022

Commonly found colonizing the human microbiota, Candida albicans is a microorganism known for its ability to cause infections, mainly in the vulvovaginal region known as vulvovaginal candidiasis (VVC). This pathology is, in fact, one of the main C. albicans clinical manifestations, changing from a colonizer to a pathogen. The increase in VVC cases and limited antifungal therapy make C. albicans an increasingly frequent risk in women’s lives, especially in immunocompromised patients, pregnant women and the elderly. Therefore, it is necessary to develop new therapeutic options, especially those involving natural products associated with nanotechnology, such as lycopene and mesoporous silica nanoparticles. From this perspective, this study sought to assess whether lycopene, mesoporous silica nanoparticles and their combination would be an attractive product for the treatment of this serious disease through microbiological in vitro tests and acute toxicity tests in an alternative in vivo model of Galleria mellonella. Although they did not show desirable antifungal activity for VVC therapy, the present study strongly encourages the use of mesoporous silica nanoparticles impregnated with lycopene for the treatment of other human pathologies, since the products evaluated here did not show toxicity in the in vivo test performed, being therefore, a topic to be further explored.
Drugs for COVID-19: An Update
Authors: Ceramella Jessica , Iacopetta Domenico , Sinicropi Maria Stefania , Andreu Inmaculada , Mariconda Annaluisa , Saturnino Carmela , Giuzio Federica , Longo Pasquale , Aquaro Stefano , Catalano Alessia
Published: December 2022

The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) was the seventh known human coronavirus, and it was identified in Wuhan, Hubei province, China, in 2020. It caused the highly contagious disease called coronavirus disease 2019 (COVID-19), declared a global pandemic by the World Health Organization (WHO) on 11 March 2020. A great number of studies in the search of new therapies and vaccines have been carried out in these three long years, producing a series of successes; however, the need for more effective vaccines, therapies and other solutions is still being pursued. This review represents a tracking shot of the current pharmacological therapies used for the treatment of COVID-19.
Epigallocatechin Gallate Attenuates Gentamicin-Induced Nephrotoxicity by Suppressing Apoptosis and Ferroptosis
Authors: Yue Lin , Yang Ya-Ru , Ma Wen-Xian , Wang Hong-Yan , Fan Qian-Wen , Wang Yue-Yue , Li Chao , Wang Jing , Hu Zi-Mu , Wang Xue-Fu , Li Feng-He , Liu Ming-Ming , Jin Juan , Shi Chao , Wen Jia-Gen
Published: December 2022

Gentamicin (GEN) is a kind of aminoglycoside antibiotic with the adverse effect of nephrotoxicity. Currently, no effective measures against the nephrotoxicity have been approved. In the present study, epigallocatechin gallate (EG), a useful ingredient in green tea, was used to attenuate its nephrotoxicity. EG was shown to largely attenuate the renal damage and the increase of malondialdehyde (MDA) and the decrease of glutathione (GSH) in GEN-injected rats. In NRK-52E cells, GEN increased the cellular ROS in the early treatment phase and ROS remained continuously high from 1.5 H to 24 H. Moreover, EG alleviated the increase of ROS and MDA and the decrease of GSH caused by GEN. Furthermore, EG activated the protein levels of nuclear factor erythroid 2-related factor 2 (Nrf2) and heme oxygenase-1 (HO-1). After the treatment of GEN, the protein level of cleaved-caspase-3, the flow cytometry analysis and the JC-1 staining, the protein levels of glutathione peroxidase 4 (GPX4) and SLC7A11, were greatly changed, indicating the occurrence of both apoptosis and ferroptosis, whereas EG can reduce these changes. However, when Nrf2 was knocked down by siRNA, the above protective effects of EG were weakened. In summary, EG attenuated GEN-induced nephrotoxicity by suppressing apoptosis and ferroptosis.
Design of a New Chiral Deep Eutectic Solvent Based on 3-Amino-1,2-propanediol and Its Application in Organolithium Chemistry
Authors: Antenucci Achille , Bonomo Matteo , Ghinato Simone , Blangetti Marco , Dughera Stefano
Published: December 2022

A chiral glycerol derivative, namely 3-amino-1,2-propanediol, was employed for as the hydrogen bond donor (HBD) in the design of a new deep eutectic solvent (DES) with choline chloride acting as the hydrogen bond acceptor (HBA). The novel mixture was characterized and unambiguously classified as a DES. Furthermore, its synthetic usefulness was demonstrated in the room-temperature n-butyllithium-addition under air to carbonyl compounds and benzyl chloride. In some cases, pure products (100% conversion) were obtained by a simple extractive work-up in up to 72% isolated yield, thus suggesting the potential practical usefulness of this procedure as a green alternative to the classical Schenk procedure in volatile organic solvents for the synthesis of tertiary alcohols. The chirality of the HBD, bearing an interesting basic primary amino group, is an intriguing feature currently under investigation for further exploitation.