Article
СИНТЕЗ И СТРУКТУРА ГИБРИДНЫХ ГАЛОВИСМУТАТОВ – ПРОИЗВОДНЫХ N-АЦЕТОНИЛПИРИДИНИЯ
New hybrid N-acetonylpyridinium, N-(ω-iodoacetonyl)pyridinium, and N-acetonyl-2,6-dimethylpyridinium halobismuthates I–VII have been synthesized and structurally characterized. A preparative method of synthesis is proposed for compounds I, III, and VII, and some individual crystals have been managed to separate and characterize for compounds II, I–VI. A new type of {K[BiBr6]}n2n- 1D-chains with K+ cations has been revealed in the structure of [C8H10NO]2K[BiBr6] (II). N-acetonyl-2,6-dimethylpyridinium bromobismuthates [C10H14NO]3[Bi2Br9] V and VI (space group P21/n) are polymorphs of similar structure. Iodobismuthates [C8H10NO]4[Bi4I16] (III) and [C10H14NO]4[Bi4I16] ⋅ 0.69I2 (VII) are built of [Bi4I16]4– anions, and [Bi4I16] moieties in the structure of VII are linked into a 1D-anionic chain by molecules I2.
A series of new type hybrid bromobismuthates formed by various pyrazinium cations were isolated and studied. In the systems initially containing iodide-anions and monocations of substituted pyrazines, the complexes on the base of doubly-charged cations of substituted pyrazines instead of ones based on corresponding monocations were surprisingly formed. The variation of substituted pyrazinium cation affects not only the crystal structures of hybrid bromobismuthates via tuning the nuclearity of the anions but also the hydrolytic stability of the compounds. Thorough structural study of hydrolytic transformations was performed for halobismuthates for the first time. The results revealed stepwise course of the process affording several products. Spectral studies of the complexes evidence that the values of optical band gaps (Eg) are low in comparison with those for similar systems which is most likely due to the cooperative effect involving the nature of the corresponding cations together with the features of the supramolecular structures of the complexes.
The following bromobismuthates of organic cations (dipyridinoalkane derivatives) are synthesized and characterized: (4-NH2PyC5)BiBr5 (I), (2-MePyC2)BiBr5 (II), (2-NH2PyC10)BiBr5 center dot 0.65H(2)O (III), (2-NH2PyC10)(4)H5O2(BiBr6)(3) (IV), (2-NH2PyD6)(2)KBi2Br11 (V), (2-NH2PyC6)H3OBiBr6 center dot 2.33H(2)O (VI), and (2-NH2PyC6)(3)(BiBr6)(2) center dot CH3CN (VII). Three compounds obtained (I-III) contain the zigzag 1D chain (BiBr5) (n) . A new type of 1D chains, (KBi2Br11) (n) , is found in the structure of compound V. Pseudo-1D chains of BiBr6 (3-) anions can be observed in the 3D structures of compounds IV, VI, and VII. The crystallographic data were deposited with the Cambridge Crystallographic Data Centre (CIF files CCDC 1569478 (I)-1569484 (VII), respectively)
Huntite-family nominally-pure and activated/co-activated LnM3(BO3)4 (Ln = La–Lu, Y; M = Al, Fe, Cr, Ga, Sc) compounds and their-based solid solutions are promising materials for lasers, nonlinear optics, spintronics, and photonics, which are characterized by multifunctional properties depending on a composition and crystal structure. The purpose of the work is to establish stability regions for the rare-earth orthoborates in crystallochemical coordinates (sizes of Ln and M ions) based on their real compositions and space symmetry depending on thermodynamic, kinetic, and crystallochemical factors. The use of diffraction structural techniques to study single crystals with a detailed analysis of diffraction patterns, refinement of crystallographic site occupancies (real composition), and determination of structure–composition correlations is the most efficient and effective option to achieve the purpose. This approach is applied and shown primarily for the rare-earth scandium borates having interesting structural features compared with the other orthoborates. Visualization of structures allowed to establish features of formation of phases with different compositions, to classify and systematize huntite-family compounds using crystallochemical concepts (structure and superstructure, ordering and disordering, isostructural and isotype compounds) and phenomena (isomorphism, morphotropism, polymorphism, polytypism). Particular attention is paid to methods and conditions for crystal growth, affecting a crystal real composition and symmetry. A critical analysis of literature data made it possible to formulate unsolved problems in materials science of rare-earth orthoborates, mainly scandium borates, which are distinguished by an ability to form internal and substitutional (Ln and Sc atoms), unlimited and limited solid solutions depending on the geometric factor.
We have performed a comparative analysis of the bio-oil produced by thermal liquefaction of microalgae in different solvents using high-resolution Orbitrap mass spectrometry and GC-MS approach. Water, methanol, ethanol, butanol, isopropanol, acetonitrile, toluene, and hexane were used as solvents in which the liquefaction was performed. It was observed that all resulting oils demonstrate a considerable degree of similarity. For all samples, compounds containing 1 and 2 nitrogen atoms dominated in the positive ESI spectra, while a relative contribution of other compounds was small. In negative ESI mode, compounds having 2 to 7 oxygens were observed. Statistical analysis revealed that products can be combined in two groups depending on the solvent used for the liquefaction. To the first group, we can attribute the products obtained by using protic (alcohols) and to the second by using aprotic (acetonitrile, toluene) solvents. Nevertheless, based on our results, we concluded that solvent possesses a minor impact on molecular composition of bio-oil. We suggested that the driving force of the liquefaction reaction is the thermal dehydration of the carbohydrate in algae, resulting in water formation, which could be the trigger of the producing of bio-oil. To prove this hypothesis, we performed the reaction with the dry algae in the absence of the solvent and observed the formation of bio-oil.
The New Russian Encyclopedia is a fundamental reference publication in 18 volumes that characterizes nature, population, economy, history, science, art, technology and other important aspects. Contains about 60,000 articles, about 30,000 biographies, about 15,000 color illustrations, maps, charts, diagrams, tables. Leaves since 2003.
Local electronic properties of quasi-two-dimensional Pb(111) islands with screw dislocations of different types on their surfaces were experimentally studied by means of low-temperature scanning tunneling microscopy and spectroscopy in the regime of constant current. A comparison of the topography map, the maps of tunneling current variation, and the differential tunneling conductance acquired simultaneously allows one to visualize the hidden parts of the dislocation loops under the sample surface. We demonstrate that two closely positioned screw dislocations with the opposite Burgers vectors can either (i) connect to each other by the sub-surface dislocation loop or (ii) generate independent hidden edge dislocation lines, which run toward the perimeter of the Pb island. In addition, we found a screw dislocation, which does not produce outcoming sub-surface dislocation loops. Screw dislocations and the hidden dislocation lines are the source of the non-quantized variation of the local thickness of the Pb terraces, affecting the local electronic properties.
This volume, being the 55th of this Series, contains a wealth of information on bioactive natural products. In Chapter 1, Watson and colleagues have discussed the synthesis of monoterpene indole alkaloids, an important class of structurally diverse natural products, with respect to conventional and biomimetic synthetic approaches.
Titanocene(III) has been widely used in the synthesis of complex organic molecules and natural products including polyketides, phenylpropanoids, antibiotics, and alkaloids. Oltra and coworkers have provided a review on the stereoselective synthesis of natural products facilitated by titanocene(III) in Chapter 2.
About 70 biologically active macrocyclic bisbibenzyls (MBBs) have been isolated and structurally elucidated during the last 30 years. Song and Zhao, in Chapter 3, have provided a review on the synthesis of MBBs with diverse pharmacological properties.
Diabetes mellitus is the most common endocrine/metabolic disorder that poses a global health concern. Reyes and colleagues have discussed the hypoglycemic activity of some terrestrial and marine bioactive compounds with potential for treating type 2 diabetes in Chapter 4. In Chapter 5, Pietruszka and coworkers have highlighted the importance of some marine oxylipins that exhibit different bioactive properties.
Depression has become a psychiatric disorder, which leads to various disabilities. Natural compounds like polyphenols and terpenoids have antioxidant and neuroprotective properties and can be used for the treatment of depression. In Chapter 6, Rodrigues et al. review the clinical studies and trials on polyphenols and terpenoids for the treatment of various psychiatric disorders. The lipid A phosphate and their phosphorylated analogues found in Gram-negative bacteria are of major importance because they provide the host with defense against infections from various microorganisms. Paradies and Zimmermann have discussed physical characteristics, isolation, and bioactivity of lipopolysaccharides (lipid A) for developing new vaccines and therapeutics in Chapter 7.
Hydroxycinnamic acids (HCAs) are a group of phytonutrients with numerous beneficial effects on human health that are largely derived from plants. HCAs play important roles like defense against UV rays or pathogenic attack during growth and development of plants. In Chapter 8, El-Seedi and colleagues present a review focusing on the therapeutic effects of HCAs for the treatment of cancer, diabetes, pulmonary, hepatic, neuro-, and cardiovascular diseases. In Chapter 9, Pomilio and Mercader have presented the study of natural anthocyanins and other related flavonoids for the readers, highlighting their possible and preferable uses as health-protecting food dyes over synthetic ones. They have also discussed the anthocyanins isolated from Ipomoea cairica along with their QSAR studies.
Cardiovascular diseases are considered to be a major threat to health. Polyphenols and carotenoids are structurally diverse groups of bioactive compounds isolated from fruits and vegetables, carrying protective effects against endothelial dysfunction. These therapeutic effects have been explored by Yamagata in Chapter 10.
The roots of licorice and ivy leaves have been used in folk medicine and drugs since long. The biological activity of these complexes has been discussed by Yakovishin and Grishkovets in Chapter 11. In Chapter 12, the chemical and biological characteristics of amicoumacins and xenocoumacins are reviewed by Korshun et al. with reference to the preparation of antibiotics.
I hope that this volume will be received with the same enthusiasm as the earlier volumes of this long-standing series the first volume of which was published under my Editorship in 1988. I would like to express my gratitude to Ms. Taqdees Malik and Mr. Mahmood Alam for their assistance in the preparation of this volume.
The hydrogenation of diphenylacetylene (DPA) on palladium–silver catalysts with a single-atom structure was investigated. It has been shown experimentally that the reaction rate of alkene to alkane hydrogenation is substantially lower than the rate of DPA semi-hydrogenation. The kinetic barriers of all stages of hydrogenation were calculated by the DFT method.