New C15 Acetogenins from Two Species of Laurencia from the Aegean Sea

The chemical diversity of the approximately 1,200 natural products isolated from red algae of the genus Laurencia, in combination with the wide range of their biological activities, have placed species of Laurencia in the spotlight of marine chemists’ attention for over 60 years. The chemical investigation of the organic (CH₂Cl₂/MeOH) extracts of Laurencia microcladia and Laurencia obtusa, both collected off the coasts of Tinos island in the Aegean Sea, resulted in the isolation of 32 secondary metabolites, including 23 C₁₅ acetogenins (1–23), 7 sesquiterpenes (24–30) and 2 diterpenes (31 and 32). Among them, six new C₁₅ acetogenins, namely 10-acetyl-sagonenyne (2), cis-sagonenyne (3), trans-thuwalenyne C (4), tinosallene A (11), tinosallene B (12) and obtusallene XI (17), were identified and their structures were elucidated by extensive analysis of their spectroscopic data. Compounds 1–3, 5–11, 13 and 15–32 were evaluated for their antibacterial activity against Staphylococcus aureus and Escherichia coli.     

Using Control Variables to Improve the Efficiency of Percentile Estimation in Stochastic Simulation

Control variables may be used in the estimation of percentiles by stochastic stimulation. Hitherto control variables have only been applied to estimating the mean of a response variable; however, in many uses of simulation, information about the tails of the distribution of a response variable are of more interest. The efficacy of the method is demonstrated by application to an example of a simulation study in capital budgeting where exposure to risk is important.     

Un teorema di esistenza per controlli ottimi di sistemi definiti da equazioni integrali di Urysohn

Summary In this paper an existence theorem is proved for optimal control problems described by Urysohn systems, with pointwise constraints on controls and states. An example of application of the existence theorem is given.

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Entrata in Redazione il 15 marzo 1978.

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Lavoro eseguito nell'ambito della mia attività di ricerca come borsista C.N.R., presso l'Università di Genova.     

Universal non-completely-continuous operators

A bounded linear operator between Banach spaces is calledcompletely continuous if it carries weakly convergent sequences into norm convergent sequences. Isolated is a universal operator for the class of non-completely-continuous operators fromL ₁ into an arbitrary Banach space, namely, the operator fromL ₁ into ⊆_∞ defined byT ₀(f) = (∫r _n f d μ) _n>-0, wherer _n is thenth Rademacher function. It is also shown that there does not exist a universal operator for the class of non-completely-continuous operators between two arbitrary Banach spaces. The proof uses the factorization theorem for weakly compact operators and a Tsirelson-like space. Supported in part by NSF grant DMS-9306460. Participant, NSF Workshop in Linear Analysis & Probability, Texas A&M University (supported in part by NSF grant DMS-9311902). Supported in part by NSF grant DMS-9003550.     

Tuning the Reactivities of the Heteronuclear [AlnV3−nO7−n]+ (n=1, 2) Cluster Oxides towards Methane by Varying the Composition of the Metal Centers

The thermal gas-phase reactions of [Al₂VO₅]⁺ and [AlV₂O₆]⁺ with methane have been explored by using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry complemented by high-level quantum chemical calculations. Both cluster ions chemisorbed methane as the major reaction channels at room temperature. [Al₂VO₅]⁺ could break only one C−H bond to liberate CH₃, whereas [AlV₂O₆]⁺ exhibited higher oxidizing ability such that it brings about the selective generation of formaldehyde. Mechanistic aspects are revealed and the crucial roles of the metal centers are discussed.     

Aromatic and Antiaromatic Pathways in Triphyrin(2.1.1) Annelated with Benzo[b]heterocycles

Understanding of the aromatic properties and magnetically induced current densities of highly conjugated chromophores is important when designing molecules with strongly delocalized electronic structure. Linear extension of the triphyrin(2.1.1) skeleton with an annelated benzo[b]heterocycle fragment modifies the aromatic character by extending the electron delocalization pathway. Two-electron reduction leads to an antiaromatic triphyrin(2.1.1) ring and an aromatic benzo[b]heterocycle subunit. Current-density calculations provide detailed information about the observed pathways and their strengths.     

A new methodology for the determination of silicon in plants by wavelength dispersive X-ray fluorescence

Silicon is an important element for plants at their structure and physiology and plays an important role in bone mineralization and soft tissue development in human beings. Furthermore, its determination is being requested more frequently due to nutritional requirements. However, the methods found in the literature to determine silicon in this type of samples require a sample preparation step, which makes them time-consuming and provides high uncertainties. In this paper, a method for the determination of silicon in plants by wavelength dispersive X-ray fluorescence (WD-XRF) spectrometry has been developed. Horsetail (Equisetum arvense L.) and nettle leaf (Urtica dioica) have been used as a source of silicon due to its medical use. Sample preparation involved calcining the sample at 700°C and preparing fused beads from the calcined sample. Calibration standards for WD-XRF measurement were prepared by mixing certified reference materials and chemical products to reproduce the samples matrix. The linear range for silicon concentration ranges from 6 to 55 wt% SiO₂. The validation of the method was performed measuring a reference material (NCS DC73349 Bush branches and leaves) and comparing the results obtained by WD-XRF with those obtained by an independent method by atomic absorption spectrometry. The developed methodology is rapid and accurate, provides low uncertainties, and is environmentally friendly, as it does require the use of less hazardous reagents.