GC–MS analysis of phenolic compounds in fuels after conversion to trifluoroacetate esters

The GC–MS characteristics of trifluoroacetate esters of phenolic compounds are discussed. Linear temperature programmed retention indices and total ion current MS response factors of over 120 phenolic esters are reported. The main GC advantages from analysis of trifluoroacetate esters as compared to plain phenols are enhanced volatility and improved resolution. For example, the elution temperature of a given phenol is typically 50 °C greater than that of the corresponding trifluoroacetate ester. Also, while retention of compounds with two trifluoroacetate groups is only moderately greater than mono esters, underivatized dihydroxy compounds are very difficult to elute from any GC column. Complete resolution of isomeric C₀-, C₁- and C₂-alkylphenol esters is readily achieved on conventional fused silica GC columns; resolution of the corresponding underivatized compounds requires specialized GC columns with low temperature limits. In general, mass spectra of trifluoroacetate esters are more characteristic of a given structure than those of the corresponding phenols and may be more rigorously interpreted towards structural elucidation. A table in the report summarizes some of the more important spectral features used in compound identification. Example applications in analysis of coal-, shale- and petroleum-derived materials are presented. Selected ion monitoring is used to determine individual phenolic components in whole distillates; reconstructed ion chromatograms are used to illustrate distributions of selected species as a function of fuel storage and thermal stress.     

Synthesis and transformations of metallocycles. 9. Regioselective and stereoselective synthesis of al-substitutedtrans-3,4-dialkylaluminocyclopentanes catalyzed by (η5-C5H5)2ZrCl2

A new stereoselective method is developed for the synthesis of 1-chloro-, 1-alkoxy-, and 1-N,N-dialkylaminoalumino-cyclopentanes from -olefins, metallic magnesium, and aluminum halides (AlCl₃, RO-AlCl₂, R₂N-AlCl₂) in the presence of catalytic amounts of Cp₂ZrCl₂ (Cp=⁵-C₅H₅). The products from hydrolysis and deuterolysis of the Al-substituted 3,4-dialkylaluminocyclopentanes (ACP) have the threo configuration.For Communication 8, see [1].Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 450054 Ufa. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1393–1397, June, 1992.     

Synthesis of 2-arylhydrazones of aliphatic fluorine-containing 1,2,3-tricarbonyl compounds and their reactions with dinucleophiles

New fluorinated 2-arylhydrazones of 1,2,3-tricarbonyl compounds were obtained by coupling fluorine-containing 3-oxo esters, 1,3-diketones, and their copper chelates with aryldiazonium chlorides. Reactions of these arylhydrazones with hydrazine hydrate, phenylhydrazine, thiosemicarbazide, and hydroxylamine gave the corresponding pyrazole and isoxazole derivatives. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 695–700, April, 1998.     

Hydrate inclusion compounds

There are three general classes of hydrate inclusion compounds: the gas hydrates, the per-alkyl onium salt hydrates, and the alkylamine hydrates. The first are clathrates, the second are ionic inclusion compounds, the third are semi-clathrates. Crystallization occurs because the H₂O molecules, like SiO₂, can form three-dimensional four-connected nets. With water alone, these are the ices. In the inclusion hydrates, nets with larger voids are stabilized by including other guest molecules. Anions and hydrogen-bonding functional groups can replace water molecules in these nets, in which case the guest species are cations or hydrophobic moieties of organic molecules. The guest must satisfy two criteria. One is dimensional, to ensure a comfortable fit within the voids. The other is functional. The guest molecules cannot have either a single strong hydrogen-bonding group, such as an amide or a carboxylate, or a number of moderately strong hydrogen-bonding groups, as in a polyol or a carbohydrate.The common topological feature of these nets is the pentagonal dodecahedra: i.e., 5¹²-hedron. These are combined with 5¹²6²-hedra, 5¹²6³-hedra, 5¹²6⁴-hedra and combinations of these polyhedra, to from five known nets. Two of these are the well-known 12 and 17 Å cubic gas hydrate structures,Pm3n, Fd3m; one is tetragonal,P4 ₂/mnm, and two are hexagonal,P6 ₃/mmc andP6/mmm. The clathrate hydrates provide examples of the two cubic and the tetragonal structures. The alkyl onium salt hydrates have distorted versions of thePm3n cubic, the tetragonal, and one of the hexagonal structures. The alkylamine hydrate structures hitherto determined provide examples of distorted versions of the two hexagonal structures.There are also three hydrate inclusion structures, represented by single examples, which do not involve the 5¹²-hedra. These are 4(CH₃)₃CHNH₂·39H₂O which is a clathrate; HPF₆·6H₂O and (CH₃)₄NOH·5H₂O which are ionic-water inclusion hydrates. In the monoclinic 6(CH₃CH₂CH₂NH₂)·105H₂O and the orthorhombic 3(CH₂CH₂)₂NH·26H₂O, the water structure is more complex. The idealization of these nets in terms of the close-packing of semi-regular polyhedra becomes difficult and artificial. There is an approach towards the complexity of the water salt structures found in the crystals of proteins.     

Active transport of Na + and K + through animal cell membranes

The transport of Na⁺ out of the cell and K⁺ into the cell against a concentration gradient is catalyzed by a (Na⁺ + K⁺)-activated ATPase. The way in which the cations pass through the cell membrane has not yet been elucidated. Studies on the ATP hydrolysis revealed a Na⁺-dependent phosphorylation of the enzyme protein; the conformation of the enzyme also appears to change. The energy required for transport of the cations against their concentration gradients is probably provided by K⁺-dependent hydrolysis of the enzyme-bound phosphate. The enzyme can synthesize ATP from inorganic phosphate and ADP on reversal of the cation concentration gradient. By keeping the enzyme in a particular conformation, the cardiac glycoside ouabain specifically inhibits the Na⁺ pump.     

Ab initio studies on several species of the formula X3YO and X3YOH

Ab initio molecular orbital calculations using both minimal and extended basis sets have been applied to two isoelectronic sets of molecules. One set corresponds to the 18 electron species H₃NO, H₃CO^– and H₃COH while the second set contains the 42 electron fluorinated molecules F₃NO, F₃CO^– and F₃COH. The geometries of these molecules have been optimized, using both the minimal STO-3G and the extended 4-31G basis sets. These comparative calculations reveal that the 4-31G basis produced structural parameters in much better agreement with experiment. The effect of includingd-orbitals in the basis set was also investigated. For the fluorinated oxides it has been found that the optimized 4-31G structures were only slightly altered by the addition ofd-orbitals. For H₃NO, on the other hand, the inclusion ofd-orbitals considerably shortens the N-O bond distance. Both H₃NO and CF₃OH, which are unknown experimentally, are theoretically predicted to be capable of existence. The electronic structures of these molecules have also been examined using electronic partitioning according to the Mulliken scheme.     

Cobalt Chalcogenide Clusters. Synthesis,Characterization and DFT Calculations of [Co4Se2(CO)10] and [Co4Te2(CO)11]. Crystal Structure of [Co8Se4(CO)16(μ‐dppa)2]

The reactions of [Co₂(CO)₈] with E(SiMe₃)₂ (E = Se, Te) in CH₂Cl₂ result in the formation of the compounds [Co₄Se₂(CO)₁₀]> ( 1 ) and [Co₄Te₂(CO)₁₁] ( 2 ), respectively. Both cluster complexes have similar molecular structures in which the cobalt atoms form four‐membered rings with μ₄‐bridging chalcogen atoms (Se and Te) above and below the plane of the metal atoms and the carbonyl ligands as either terminal or μ₂‐bridging ligands. DFT‐calculations for both compounds have been carried out in order to obtain some more information about their electronic distribution. In the presence of the phosphine Ph₂PC≡CPPh₂ (dppa), the reaction of [Co₂(CO)₈] with Se(SiMe₃)₂ leads to the formation of [Co₈Se₄(CO)₁₆(μ‐dppa)₂] ( 3 ). During the reaction two molecules of [Co₂(CO)₈] have been added to the acetylene groups of the dppa ligands, whilst the remaining cobalt atoms coordinate to the phosphorus atoms of the phosphine. In this compounds the selenium atoms act as μ₃‐ligands, bridging the metal atoms bonded to the phosphorus with those bonded to the acetylene groups.     

Plant-Derived Natural Products as Lead Agents against Common Respiratory Diseases

Never has the world been more challenged by respiratory diseases (RDs) than it has witnessed in the last few decades. This is evident in the plethora of acute and chronic respiratory conditions, ranging from asthma and chronic obstructive pulmonary disease (COPD) to multidrug-resistant tuberculosis, pneumonia, influenza, and more recently, the novel coronavirus (COVID-19) disease. Unfortunately, the emergence of drug-resistant strains of pathogens, drug toxicity and side effects are drawbacks to effective chemotherapeutic management of RDs; hence, our focus on natural sources because of their unique chemical diversities and novel therapeutic applications. This review provides a summary on some common RDs, their management strategies, and the prospect of plant-derived natural products in the search for new drugs against common respiratory diseases.     

Virtual Screening and Hit Selection of Natural Compounds as Acetylcholinesterase Inhibitors

Acetylcholinesterase (AChE) is one of the classical targets in the treatment of Alzheimer’s disease (AD). Inhibition of AChE slows down the hydrolysis of acetycholine and increases choline levels, improving the cognitive function. The achieved success of plant-based natural drugs acting as AChE inhibitors, such as galantamine (GAL) from Galanthus genus and huperzine A from Huperzia serrate (approved drug in China), in the treatment of AD, and the fact that natural compounds (NCs) are considered as safer and less toxic compared to synthetic drugs, led us to screen the available NCs (almost 150,000) in the ZINC12 database for AChE inhibitory activity. The compounds were screened virtually by molecular docking, filtered for suitable ADME properties, and 32 ligands from 23 structural groups were selected. The stability of the complexes was estimated via 1 μs molecular dynamics simulation. Ten compounds formed stable complexes with the enzyme and had a vendor and a reasonable price per mg. They were tested for AChE inhibitory and antioxidant activity. Five compounds showed weak AChE inhibition and three of them exhibited high antioxidant activity.     

Assessment of Chemical Composition and Anti-Penicillium Activity of Vapours of Essential Oils from Abies Alba and Two Melaleuca Species in Food Model Systems

The possibilities of the practical utilization of essential oils (EOs) from various plant species in the food industry have attracted the attention of the scientific community. Following our previous studies, the antifungal activities of three further commercial EOs, Melaleuca armillaris subsp. armillaris (rosalina; REO), Melaleuca quinquenervia (niaouli; NEO), and Abies alba (fir; FEO), were evaluated in the present research in respect to their chemical profiles, over four different concentrations, 62.5 μL/L, 125 μL/L, 250 μL/L, and 500 μL/L. The findings revealed that the major compounds of REO, NEO, and FEO were linalool (47.5%), 1,8-cineole (40.8%), and α-pinene (25.2%), respectively. In vitro antifungal determinations showed that the inhibition zones of a Penicillium spp. mycelial growth ranged from no inhibitory effectiveness (00.00 ± 00.00 mm) to 16.00 ± 1.00 mm, indicating a very strong antifungal activity which was detected against P. citrinum after the highest REO concentration exposure. Furthermore, the in situ antifungal efficacy of all EOs investigated was shown to be dose-dependent. In this sense, we have found that the highest concentration (500 µL/L) of REO, NEO, and FEO significantly reduced (p < 0.05) the growth of all Penicillium strains inoculated on the bread, carrot, and potato models. These results indicate that the investigated EOs may be promising innovative agents in order to extend the shelf life of different types of food products, such as bread, carrot and potato.