Revisiting the structure of Heliannuol L: A computational approach

Recently, structural elucidation of natural products has undergone a revolution. The combined use of different modern spectroscopic methods has allowed obtaining a complete structural assignment of natural products using small amounts of sample. However, despite the extraordinary ongoing advances in spectroscopy, the mischaracterization of natural products has been and remains a recurrent problem, especially when the substance presents several stereogenic centers. The misinterpretation of nuclear magnetic resonance (NMR) data has resulted in frequent reports addressing structural reassignment. In this context, a great effort has been devoted to developing quantum chemical calculations that simulate NMR parameters accurately, allowing to achieve a more precise spectral interpretation. In this work, we employed a protocol for theoretical calculations of ¹H NMR chemical shifts and coupling constants using density functional theory (DFT), followed by the application of the DP4+ method to revisit the structure of Heliannuol L, a member of the Heliannuol class, isolated from Helianthus annuus. Our results indicate that the originally proposed structure of Heliannuol L needs a stereochemical reassignment, placing the hydroxyl bonded to C10 in the opposite side of the methyl and hydroxyl groups bonded to C7 and C8, respectively.     

Isomorfismi tra le strutture subnormali dei gruppi

Summary In this paper order-isomorphisms between subnormal structures of subsoluble groups are considered, and the images of generalized nilpotent groups in such isomorphisms are studied. A result of Pazderski about the Fitting subgroup of finite soluble groups is also extended to the upper Baer series of subsoluble groups, and an extension to infinite groups of a theorem of Heineken about isomorphisms between lattices of subnormal subgroups of finite groups is given.

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Lavoro eseguito nell'ambito del G.N.S.A.G.A. del C.N.R.     

Some functional inequalities for complete elliptic integrals

We establish some monotonicity results and inequalities involving elliptic integrals of the first and the second kind. Work sponsored by the Ministero dell’Università e della Ricerca Scientifica e Tecnologica of Italy.     

Comparison of microbial activity in some Brazilian soils by microcalorimetric and respirometric methods

The microbial activity in a Rhodic eutrudox (R), a Typic eutrudox (V) and a Quartzipsamment (Q) was monitored by respirometric and calorimetric methods. CO₂ evolution was monitored for 98 days by titrimetry and conductimetry for control amended samples (A) with 25% of cattle manure (E), municipal refuse compost (L), earthworm casts (H) or 1.25 kg ha⁻¹ of trifluralin (T). Average values of all treatments through respiration at the end of the incubation period were 5.24±0.34, 6.13±0.31 and 6.50±0.33, in mg CO₂ g⁻¹ soil, for R, V and Q, respectively, by titrimetry and 8.89±0.44, 10.41±0.54 and 10.41±0.52, in mg CO₂ g⁻¹ soil, for R, V and Q, respectively, for conductimetry. Excellent correlation (r=1.00) between titrimetry and conductimetry was observed. The decreasing order for respiration was E, H, L and T. After each incubation time, the conductimetric values were higher than those for titrimetry, for all treatments of these Brazilian soils. Average values of the exothermic thermal effect were: 0.58±0.02, 0.60±0.02 and 0.67±0.01 kJ g⁻¹ soil, for R, V and Q, respectively, for 103 days. A significant correlation coefficient of 0.91 and P<0.0001 between calorimetric and respirometric values over 98 days was observed. Based on the obtained calorimetric results, it can be proposed that this technique should be as a useful analytical method for determining the microbial activity in soils.     

On automorphisms fixing non-normal subgroups of groups

This work was carried out when the last named author visited the Department of Mathematics of the University of Napoli Federico II in March 1994. He is very grateful for the hospitality he enjoyed and for the support by the C.N.R.     

Groups with many normal-by-finite subgroups

A subgroup of a group is said to be normal-by-finite if the core of in has finite index in . In this article groups satisfying the minimal condition on subgroups which are not normal-by-finite and groups with finitely many conjugacy classes of subgroups which are not normal-by-finite are characterized.

     

Spontaneous dehydration mechanism of aromatic aldehyde reactions with hydroxyl and non‐hydroxyl amines

The plot of rate constants vs. pH for the dehydration step of the reaction between furfural and 5‐nitrofurfural with hydroxylamine, N‐methylhydroxylamine, and O‐methylhydroxylamine, shows two regions corresponding to the oxonium ion‐catalyzed and spontaneous dehydration. The oxonium ion‐catalyzed dehydration region of the reaction of furfural with the above mentioned hydroxylamines exhibits general acid catalysis with excellent Brønsted correlation (Brønsted coefficients: 0.76 (r = 0.986), 0.68 (r = 0.987), and 0.67 (r = 0.993) respectively). However, the rate constants of the spontaneous dehydration of these hydroxylamines, where water is considered the general acid catalyst, exhibit a large positive deviation from the Brønsted line. This fact was not observed in the reaction of non‐hydroxyl amines with different aromatic aldehydes by other authors, thus supporting that the spontaneous dehydration steps for these reactions proceed by intramolecular catalysis. The mechanism of intramolecular catalysis might be stepwise. First, a zwitterionic intermediate is formed. It can then evolve in the second step by loss of water, or follow a concerted pathway, with the transference of a proton through a five‐membered ring (general intramolecular acid catalysis). In the case of non‐hydroxyl amines, data suggested the possibility of a mechanism of intramolecular proton transfer through one or two water molecules, from the nitrogen of the amine to the leaving hydroxide ion. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 685–692, 2002     

Simple and effective gas chromatographic mass spectrometric procedure for the speciation analysis of organotin compounds in specimens of marine mussels. An evaluation of the organotin pollution of the lagoon of venice

This paper describes a simple, effective analytical procedure, based on a gas chromatographic mass spectrometric technique, for the speciation analysis of organotin compounds (OTC) in mussel samples. The direct alkylation reaction of the organotin chlorides in the aqueous digestion solution by NaBEt(4) allowed a short analysis time and a good recovery. The evaluation of the yield of each step constituting the analytical procedure indicated that the alkylation step is the most critical one. The proposed method was advantageously utilised to monitor the level of OTC pollution of the Lagoon of Venice. All the sites examined, both near to and far from anthropogenic activities, revealed significant levels of OTC pollution.     

Amperometric Glucose Determination by Means of Glucose Oxidase Immobilized on a Cellulose Acetate Film: Dependence on the Immobilization Procedures

Glucose microelectrodes were prepared by immobilizing glucose oxidase onto a cellulose acetate film coating a platinum wire. Hexamethylenediamine (HMDA) and Glutaraldehyde (GA) were employed as spacer and coupling agent, respectively. Sensitivities and linear response ranges were studied as a function of the relative amounts of HMDA and GA. The best sensitivity was found when HMDA and GA were 5% and 2.5% in aqueous solutions, respectively. Taking as a reference the functioning of this biosensor, the roles of HMDA and GA percentages appear to be opposed when the extension of the linear response range is considered. Indeed, an increase of one unit in HMDA percentage (from 5 to 6 %) induces an increase in the extension of the linear response range equal to that obtained with a decrease of one unit of GA percentage (from 2.5 to 1.5%).     

Non-linear and non-constant variance calibration curves in analysis of volatile organic compounds for testing of water by the purge-and-trap method coupled with gas chromatography/mass spectrometry

Currently used operating conditions for analysing volatile organic compounds (VOCs) by purge-and-trap gas chromatography/mass spectrometry (GC/MS) produced non-linear calibration curves with non-uniform variance. Second-order polynomial models therefore had to be used in weighted regression analysis of measurements of replicates spiked at various concentrations. A transparent procedure based on a reported method of very low computational complexity allowed calculation of the parameters of second-order models, confidence bands of regression lines, prediction bands, and confidence intervals of discriminated analyte concentrations. Tolerance intervals were introduced for this last purpose. Critical, detection and quantification levels drawn from the calibration curves were compared with those calculated by the EPA method.