Alicyclic Alcohols Research Articles

STUDY OF THE COMPOSITION OF BIOLOGICALLY ACTIVE FORMS OF SEA BUCKTHORN (HIPPOPHAE RHAMNOIDES L.) LEAVES BY GC-MS

Hippophae rhamnoides L. is a perennial shrub of the Elaegnaceae family, which has a significant distribution area (both in cultivation and in the wild) and an annually renewable raw material base (fruits and leaves). The leaves of sea buckthorn are characterized by a high accumulation of various groups of biologically active substances. However, the fraction of lipophilic biologically active substances of this type of medicinal plant material remains poorly understood in terms of composition and pharmacological properties. The aim of the work was to study the phytochemical composition of the lipophilic fractions of sea buckthorn leaves by GC/MS with a predictive in silico assessment of promising types of pharmacological activity of the identified compounds for the subsequent targeted development of medicinal herbal preparations based on this medicinal plant material with a certain spectrum of action. The object of the study was the leaves of three phenological phases of plant life collected in the territory of the Voronezh region and dried by the air-shadow method to a residual moisture content of not more than 10% in 2022. On the chromatograms in the leaves harvested in different phenophases of development, the presence of peaks of about 40 compounds is observed – 20 each in the preparations removed from the leaves of phases I and III; 16 – phases II of blanks, of which 14 compounds were identified – 7, 8, and 10 in phenophases I, II, and III, respectively.The greatest number of compounds of the group of sugars, sterols, aliphatic and alicyclic alcohols was typical for the leaves of the phenological phase III – the phase of technical maturity of the fruit, which is due to the accumulation of these biologically active substances in the process of life. However, leaves already in the first phase of harvesting can be considered as a potential source of vitamins and sterols due to their significant accumulation. The results of the in silico study position phytosterols (betulin and γ-sitosterol) as the target group of biologically active substances in the lipophilic fraction of the leaves of the third phase of the harvest due to the large accumulation and the presence of a high probability of hypolipidemic, hypocholesterolemic and hepatoprotective activities. At the same time, the maximum accumulation of this fraction in the leaves during the harvesting period of fruits, the main pharmacopoeial valuable raw material of this plant, contributes to the possibility of waste-free rational use of plant resources.

Core–Shell Catalysts for Conventional Oxidation of Alcohols: A Brief Review

This review highlights recent research on the application of core–shell structured materials as catalysts in the oxidation of alcohols to value-added products, such as benzaldehyde, acetophenone, benzophenone, cinnamaldehyde, and vanillin, among others. While the application of various unconventional energy inputs (such as microwave and ultrasound irradiation) was reported, this paper focuses on conventional heating. The oxidation of homocyclic aromatic, heterocyclic aromatic, aliphatic, and alicyclic alcohols catalyzed by core–shell composite catalysts is addressed. This work also highlights some unique advantages of core–shell nanomaterial catalysis, namely the flexibility of combining individual functions for specific purposes as well as the effect of various parameters on the catalytic performance of these materials.

Ion-Molecular Derivatization Reactions of Alcohols in a “Direct Analysis in Real Time” (DART) Mass Spectrometer: 4-N,N-Dimethylaminopyridine as a New Efficient Reagent

Gas-phase on-line derivatization in the ion source of a DART mass spectrometer is a new approach to the efficient detection of alcohols in complex matrices. It does not require any special sample handling; it is based just on mixing an alcohol with a nitrogen-containing compound with high proton affinity. The resulting N-alkyl-derivatized cations appear in DART spectra as very characteristic and highly intense signals. In addition to the earlier used pyridine and quinoline, we propose a new reagent, 4-N,N-dimethylaminopyridine (4-DMAP), having a higher proton affinity. It is shown that DART mass spectra recorded for alcohols in the presence of an equimolar mixture of pyridine and 4-DMAP reveal peaks that are mainly due to the 4-DMAP quaternization cation. This indicates a highly competitive ability of this reagent to get protonated and then predominantly participate in ion-molecular reactions with alcohols under study. It is suggested that 4-DMAP provides high sensitivity in the analysis of aliphatic and alicyclic primary and secondary alcohols.

Scientific Opinion on Flavouring Group Evaluation 73, Revision 5 (FGE.73Rev5): consideration of alicyclic alcohols, aldehydes, acids and related esters evaluated by JECFA (59th, 63rd and 86th meeting) and structurally related to substances evaluated in FGE.12Rev5

The EFSA Panel on Food Additives and Flavourings was requested to evaluate 24 flavouring substances assigned to the Flavouring Group Evaluation 73 (FGE.73), using the Procedure as outlined in the Commission Regulation (EC) No 1565/2000. Twenty-three substances have already been considered in FGE.73 and its four revisions ([FL-no: 02.114, 02.141, 05.098, 05.112, 08.067, 09.289, 09.488, 09.534, 09.615, 05.119, 05.123, 08.034, 08.060, 09.028, 09.536, 05.104, 09.034, 09.712, 09.305, 02.060, 02.091, 09.278, 09.302]). The remaining substance myrtenal [FL-no: 05.106] has been cleared with respect to genotoxicity in FGE.208Rev3 and is considered in this revision 5 of FGE.73. The substances were evaluated through a stepwise approach that integrates information on the structure–activity relationships, intake from current uses, toxicological threshold of concern (TTC), and available data on metabolism and toxicity. The Panel concluded that none of these 24 substances gives rise to safety concerns at their levels of dietary intake, estimated on the basis of the ‘Maximised Survey-derived Daily Intake’ (MSDI) approach. Besides the safety assessment of the flavouring substances, the specifications for the materials of commerce have also been considered and found adequate for 23 substances. For [FL-no: 09.278], the stereoisomeric composition is not specified. For two substances [FL-no: 09.034, and 09.712], the modified Theoretical Added Maximum Daily Intake (mTAMDI) estimates are above the TTC for their structural class (I). For 17 substances evaluated through the Procedure, no normal and maximum use levels are available. Therefore, for these 19 substances, more detailed data on uses and use levels should be provided in order to refine their exposure assessments and to finalise their safety evaluations.

UV light promoted 'Metal'/'Additive'-free oxidation of alcohols: investigating the role of alcohols as electron donors.

UV light promoted selective oxidation of primary and secondary alcohols has been demonstrated under ‘metal-free’ and ‘additive-free’ conditions. Under the optimized conditions, a variety of aromatic, heteroaromatic, and alicyclic alcohols have been examined for their transformations to the corresponding carbonyl compounds. The mechanistic studies emphasize the important role of substrate (alcohol) and solvent (DMSO) in the generation of superoxide radical which is a vital intermediate for the transformation. This study also highlights the role of air as the oxidant in the oxidation process. Further, the practical application of the strategy has also been demonstrated for the oxidation of the alcoholic moiety in cholesterol.

Micellar catalysed and heteroaromatic base promoted rate enhancement of oxidation of an alicyclic alcohol in aqueous medium

Under pseudo 1st order reaction condition cyclohexanol, an alicyclic alcohol produces cyclohexanone with a moderate rate of oxidation. Promoters and surfactants enhanced the rate of oxidation with chromic acid. The product is confirmed by melting point study; 2, 4 DNP test; IR and NMR study. Among the three micellar catalyst SDS shows higher rate where as phen promoted reaction shows smaller half life. Combination of SDS and bpy shows a 600 fold enhancement in the rate of the reaction. NMR study is also carried out to confirm the interaction between the surfactants and cyclohexanol.

Metal-ligand cooperativity in a ruthenium(II) complex of bis-azoaromatic ligand for catalytic dehydrogenation of alcohols

Herein a new Ru-phosphine complex (1) with molecular formula [RuL(PPh3)Cl2] is reported where L is a redox active pincer ligand 2,6-bis(phenylazo)pyridine. The isolated complex has been characterized by usual spectroscopic techniques including single crystal X-ray crystallographic analysis. Complex 1 efficiently catalyzes aerobic oxidation of a wide range of primary and secondary benzylic, allylic, heterocyclic, alicyclic alcohols under mild conditions and is found to be superior over several other Ru (0, +2 and +3), Ru-H and Ru-PPh3 catalysts. Mechanistic studies indicate that a transient Ru-H intermediate is formed in the catalytic cycle which gets switched into a Ru-hydrazo intermediate via hydrogen-walking mechanism. The catalyst is regenerated by aerial oxidation producing H2O2 as a by-product.

Features of the First and Second Order Electrospray Ionization Mass Spectra for Salt-Like Products Derived from Monools and Diols Using Combined Reagents Based on ω-Bromoacyl Chlorides and Nitrogen Bases

Derivatization by composite reagents based on ω-bromoacyl chlorides [ClCO(C2) n Br (n = 1–4)] and pyridine was applied to study aliphatic and alicyclic alcohols and diols by ordinary and tandem electrospray ionization (ESI) mass spectrometry. The applied derivatization involves the simultaneous acylation of hydroxyl groups with an acyl chloride moiety and the quaternization of pyridine with a terminal bromoalkyl group. Under the ESI conditions, quaternary salts produce corresponding mono and diammonium cations, which are detected in the first-order mass spectra. Collision-induced dissociation (CID) of primary cations generated from monool derivatives gives rise to ammonium cations of the corresponding acids HOOC(CH2) n –N+(C5H5). The CID of primary dications affords the same cations which are also eliminated from dications to form mono-charged fragments.

Scientific Opinion on Flavouring Group Evaluation 73, Revision 4 (FGE.73Rev4): consideration of alicyclic alcohols, aldehydes, acids and related esters evaluated by JECFA (59th and 63rd meeting) structurally related to primary saturated or unsaturated alicyclic alcohols, aldehydes, acids and esters evaluated by EFSA in FGE.12Rev5.

The EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (JECFA), and to decide whether further evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present revision of FGE.73 concerns the inclusion of four additional flavouring substances (p‐mentha‐1,8‐dien‐7‐ol [FL‐no: 02.060], myrtenol [FL‐no: 02.091], p‐mentha‐1,8‐dien‐7‐yl acetate [FL‐no: 09.278] and myrtenyl acetate [FL‐no: 09.302]) evaluated by JECFA at the 59th meeting. The substances were evaluated through a stepwise approach integrating information on structure–activity relationships, intake from current uses, toxicological thresholds of concern (TTC), and available data on metabolism and toxicity. In agreement with JECFA, the Panel evaluated 22 and one candidate substances via the A and the B‐side of the Procedure, respectively, and concluded for all substances ‘No safety concern at estimated levels of intake as flavouring substances’ based on the maximised survey‐derived daily intake (MSDI) approach. The specifications for the materials of commerce have also been considered. Adequate specifications, including complete purity criteria and identity data, are available for 22 out of the 23 JECFA substances evaluated in this FGE. For [FL‐no: 09.278], the stereoisomeric composition is not specified. For the six substances with [FL‐no: 02.060, 02.091, 09.034, 09.278, 09.302 and 09.712] evaluated in this FGE, use levels have become available and the modified theoretical added maximum daily intakes (mTAMDIs) were estimated. For two substances [FL‐no: 09.034, and 09.712], the mTAMDI estimates were above the TTC for their structural class and more detailed information is needed to finalise their evaluation. For the remaining 17 substances evaluated through the Procedure, use levels are needed to calculate the mTAMDIs in order to identify those flavouring substances that need more refined exposure assessment in order to finalise the evaluation.

Leishmanicidal Activity and Structure-Activity Relationships of Essential Oil Constituents.

Several constituents of essential oils have been shown to be active against pathogens such as bacteria, fungi, and protozoa. This study demonstrated the in vitro action of ten compounds present in essential oils against Leishmania amazonensis promastigotes. With the exception of p-cymene, all evaluated compounds presented leishmanicidal activity, exhibiting IC50 between 25.4 and 568.1 μg mL−1. Compounds with the best leishmanicidal activity presented a phenolic moiety (IC50 between 25.4 and 82.9 μg mL−1). Alicyclic alcohols ((−)-menthol and isoborneol) and ketones ((−)-carvone) promoted similar activity against the parasite (IC50 between 190.2 and 198.9 μg mL−1). Most of the compounds showed low cytotoxicity in L929 fibroblasts. Analysis of the structure-activity relationship of these compounds showed the importance of the phenolic structure for the biological action against the promastigote forms of the parasite.

A gas chromatography/mass spectrometry study of the conversion of alicyclic alcohols on membrane-type catalysts using a pulse microreactor implanted into a gas chromatograph injector

A pulse microreactor implanted directly into a gas chromatograph injector combined with a mass spectrometer has been proposed for monitoring the activity of heterogeneous catalysts. The microreactor was made of a standard commercial liner for a particular gas chromatograph and contained a catalytic bed. A heated injector oven was used simultaneously for heating the catalytic region, rapid evaporation of the substrate, and pulsed introduction of reaction products into a chromatographic column. The temperature of the oven could be varied in the range 200–300°C. The method ensures the detailed description of the qualitative composition of the reaction products. The potential of the proposed microreaction system was demonstrated in the study of membrane-type catalysts (nanodiamonds modified by Pt–Ru and Pt–Ni and also catalytic phosphate systems with NASICON structure) in reactions of cyclohexanol, cyclopentanol, and cyclobutanol. The studied heterogeneous catalysts can be divided in two groups. One group (based on nanodiamonds) promotes dehydrogenation reactions. The NASICON catalytic group catalyzes dehydration reactions with the formation of cycloalkenes and dicycloalkyl ethers.

ChemInform Abstract: IPSO‐Hydroxylation of Boronic Acid via Ozonolysis: A Metal‐, Ligand‐, and Base‐Free Method.

Here, we have developed a simple, efficient, and metal-, ligand-, and base-free method for the synthesis of functionalized aryl and alicyclic alcohols via ozonolysis of corresponding boronic acids in aqueous ethanol. The procedure is compatible with a variety of functional groups and can be utilized as an alternative method for the synthesis of hydroxy arenes and alicyclic alcohols.Here, we have developed a simple, efficient, and metal-, ligand-, and base-free method for the synthesis of functionalized aryl and alicyclic alcohols via ozonolysis of corresponding boronic acids in aqueous ethanol. The procedure is compatible with a variety of functional groups and can be utilized as an alternative method for the synthesis of hydroxy arenes and alicyclic alcohols.

Health effects from spilled chemical deemed unlikely

A federal study of 4-methylcyclohexanemethanol (MCHM) concluded this month that exposure to the chemical through the Charleston, W.Va., water supply in 2014 is “not likely to be associated with any adverse health effects.” MCHM was the largest component of a mixture of chemicals that leaked from a corroded commercial storage tank upstream of the water supply for some 300,000 people. City officials issued a ban on the use of tap water for drinking and washing that lasted more than a week for some of the affected residents. Lack of information about MCHM, an alicyclic alcohol used to process coal, and other components of the spilled liquid led the Centers for Disease Control & Prevention (CDC) to request further study from the National Toxicology Program (NTP). “Alicyclic alcohols and other chemicals of this sort are likely to have similar toxicological properties,” says Scott S. Auerbach, a molecular toxicologist who worked on

Safety and efficacy of secondary alicyclic saturated and unsaturated alcohols, ketones, ketals and esters with ketals containing alicyclic alcohols or ketones and esters containing secondary alicyclic alcohols from chemical group 8 when used as flavourings for all animal species

Safety and efficacy of secondary alicyclic saturated and unsaturated alcohols, ketones, ketals and esters with ketals containing alicyclic alcohols or ketones and esters containing secondary alicyclic alcohols from chemical group 8 when used as flavourings for all animal species

IPSO-Hydroxylation of Boronic Acid via Ozonolysis: A Metal-, Ligand-, and Base-free Method

Here, we have developed a simple, efficient, and metal-, ligand-, and base-free method for the synthesis of functionalized aryl and alicyclic alcohols via ozonolysis of corresponding boronic acids in aqueous ethanol. The procedure is compatible with a variety of functional groups and can be utilized as an alternative method for the synthesis of hydroxy arenes and alicyclic alcohols.Here, we have developed a simple, efficient, and metal-, ligand-, and base-free method for the synthesis of functionalized aryl and alicyclic alcohols via ozonolysis of corresponding boronic acids in aqueous ethanol. The procedure is compatible with a variety of functional groups and can be utilized as an alternative method for the synthesis of hydroxy arenes and alicyclic alcohols.

Scientific Opinion on Flavouring Group Evaluation 9, Revision 6 (FGE.09Rev6): Secondary alicyclic saturated and unsaturated alcohols, ketones and esters containing secondary alicyclic alcohols from chemical group 8 and 30, and an ester of a phenol derivative from chemical group 25

The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to evaluate 22 flavouring substances in the Flavouring Group Evaluation 9, Revision 6, using the Procedure in Commission Regulation (EC) No 1565/2000. None of the substances was considered to have genotoxic potential. The substances were evaluated through a stepwise approach (the Procedure) that integrates information on structure–activity relationships, intake from current uses, toxicological threshold of concern and available data on metabolism and toxicity. The present revision of FGE.09 includes the assessment of one additional flavouring substance, trans-3-methyl-2-(2-pentenyl)-2-cyclopenten-1-one [FL-no: 07.219]. The Panel concluded that the 22 substances [FL-nos: 02.070, 02.075, 02.135, 02.167, 06.136, 07.059, 07.109, 07.202, 07.203, 07.219, 07.255, 09.154, 09.355, 09.520, 09.618, 09.619, 09.621, 09.843, 09.870, 09.929, 09.935 and 09.949] do not give rise to safety concerns at their levels of dietary intake, estimated on the basis of the MSDI approach. However, based on mTAMDI calculations, for 11 flavouring substances [FL-nos: 07.059, 07.109, 07.202, 07.203, 09.154, 09.520, 09.618, 09.619, 09.843, 09.935 and 09.949] more reliable exposure data are required for a re-evaluation. For two substances [FL-nos: 07.219 and 09.929] no use levels are available and these should be submitted. Besides the safety assessment of these flavouring substances, the specifications for the materials of commerce have been considered. Specifications, including complete purity criteria and identity for the materials of commerce, have been provided for all candidate substances.

Optical, Electrochemical and Thermoanalytical Investigations on Newly-Synthesized Perylene-3,4,9,10-Dianhydride Fluorescent Dyes.

A series of dyes using tetrachloroperylene dianhydride as fluorescent chromophore was synthesized by the substitution of suitable aliphatic and alicyclic alcohols in alkaline medium, and evaluation of dyes was done for their optical, electrochemical and thermal properties. These dyes exhibited absorption maxima λmax in the range of 440-460nm in aqueous medium due to the presence of highly-conjugated framework. Fluorescence spectra of these dyes in water showed sharp emission peaks with small bandwidths and large fluorescence rate constants, i e., 1.36 × 10(8) to 2.25 × 10(8)S(-1). Redox potential E1/2 and band gap energy Eg were observed in the range of -0.689 to -0.784 and 2.530 to 2.610eV, respectively. Thermal stability was noticed up to 300°C on the basis of TG and DTA findings. The structures of perylene-azo dyes were confirmed by FTIR and NMR spectroscopy. Graphical Abstract Optical, electrochemical and thermoanalytical investigations on newly-synthesized perylene-3,4,9,10-dianhydride fluorescent dyes.

Characterization of hamster NAD+-dependent 3(17)β-hydroxysteroid dehydrogenase belonging to the aldo-keto reductase 1C subfamily.

The cDNAs for morphine 6-dehydrogenase (AKR1C34) and its homologous aldo-keto reductase (AKR1C35) were cloned from golden hamster liver, and their enzymatic properties and tissue distribution were compared. AKR1C34 and AKR1C35 similarly oxidized various xenobiotic alicyclic alcohols using NAD(+), but differed in their substrate specificity for hydroxysteroids and inhibitor sensitivity. While AKR1C34 showed 3α/17β/20α-hydroxysteroid dehydrogenase activities, AKR1C35 efficiently oxidized various 3β- and 17β-hydroxysteroids, including biologically active 3β-hydroxy-5α/β-dihydro-C19/C21-steroids, dehydroepiandrosterone and 17β-estradiol. AKR1C35 also differed from AKR1C34 in its high sensitivity to flavonoids, which inhibited competitively with respect to 17β-estradiol (Ki 0.11-0.69 μM). The mRNA for AKR1C35 was expressed liver-specific in male hamsters and ubiquitously in female hamsters, whereas the expression of the mRNA for AKR1C34 displayed opposite sexual dimorphism. Because AKR1C35 is the first 317Β-HYDROXYSTEROID DEHYDROGENASE IN THE AKR SUPERFAMILY: , we also investigated the molecular determinants for the 3β-hydroxysteroid dehydrogenase activity by replacement of Val54 and Cys310 in AKR1C35 with the corresponding residues in AKR1C34, Ala and Phe, respectively. The mutation of Val54Ala, but not Cys310Phe, significantly impaired this activity, suggesting that Val54 plays a critical role in recognition of the steroidal substrate.

Structure–activity relationship of flavonoids as potent inhibitors of carbonyl reductase 1 (CBR1)

Human carbonyl reductase 1 (CBR1), a member of the short-chain dehydrogenase/reductase superfamily, reduces a variety of carbonyl compounds including therapeutic drugs. CBR1 is involved in the reduction of the anthracycline anticancer drugs to their less anticancer C-13 hydroxy metabolites, which are cardiotoxic. CBR1 inhibitors are thought to be promising agents for adjuvant therapy with twofold beneficial effect in prolonging the anticancer efficacy of the anthracyclines while decreasing cardiotoxicity, a side effect of the drugs. In this study, we evaluated 27 flavonoids for their inhibitory activities of CBR1 in order to explore the structure–activity relationship (SAR). Among them, luteolin (2-(3,4-dihydroxyphenyl)-5,7-dihydroxy-4H-1-benzopyran-4-one) showed the most potent inhibition (IC5095nM), which is also more potent compared to all known classes of CBR1 inhibitors. The inhibition of luteolin was noncompetitive with respect to the substrate in the NADPH-dependent reduction direction, but CBR1 exhibited moderate NADP+-dependent dehydrogenase activity for some alicyclic alcohols, in which the luteolin inhibition was competitive with respect to the alcohol substrate (Ki59nM). The SAR of the flavonoids indicated that the 7-hydroxy group of luteolin was responsible for the potent inhibition of CBR1. The molecular docking of luteolin in CBR1–NADPH complex showed that theflavonoid binds to the substrate-binding cleft, in which its 7-hydroxy group formed a H-bond with main-chain oxygen of Met234, in addition to H-bond interactions (of its 5-hydroxy and 4-carbonyl groups with catalytically important residues Tyr193 and/or Ser139) and a π-stacking interaction (between its phenyl ring and Trp229).

Scientific Opinion on Flavouring Group Evaluation 12, Revision 5 (FGE.12Rev5): Primary saturated or unsaturated alicyclic alcohol, aldehyde, acid, and esters from chemical groups 1, 7 and 8)

The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to evaluate 15 flavouring substances in the Flavouring Group Evaluation 12, Revision 5, using the Procedure in Commission Regulation (EC) No 1565/2000. This revision is made due to the inclusion of the assessment of three additional candidate substances, beta-isomethylionone [FL-no: 07.041], 4-(2,5,6,6-tetramethyl-1-cyclohexenyl)but-3-en-2-one [FL-no: 07.200] and tr-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)but-2-en-1-one [FL-no: 07.224], compared to FGE.12Rev4. These three substances have been cleared for a genotoxic concern in FGE.213Rev1 and can accordingly be evaluated using the Procedure in the present revision of FGE.12. The 15 substances were evaluated through a stepwise approach (the Procedure) that integrates information on structure-activity relationships, intake from current uses, toxicological threshold of concern, and available data on metabolism and toxicity. The Panel concluded that all 15 flavouring substances [FL-no: 02.134, 02.186, 02.216, 02.217, 05.157, 05.182, 05.183, 05.198, 07.041, 07.200, 07.224, 08.135, 09.342, 09.670 and 09.829] do not give rise to safety concerns at their levels of dietary intake, estimated on the basis of the MSDI (Maximised Survey-derived Daily Intake) approach. Besides the safety assessment of these flavouring substances, the specifications for the materials of commerce have also been considered. Adequate specifications including complete purity criteria and identity for the materials of commerce have been provided for all 15 candidate substances.