Isotope dilution method for the assay of rotenone in olive oil and river waters by liquid chromatography/multiple reaction monitoring tandem mass spectrometry

A new approach for the assay of rotenone (1) by isotope dilution mass spectrometry is presented. The extreme toxicity of rotenone, a natural phytodrug with insecticidal and piscicidal activity, recently banned by national and international environmental protection agencies, calls for the development of sensitive and accurate methods of analyses. Accordingly, the proposed protocol is based on the availability of the labeled internal standard rotenone‐d₃ (3) which can be conveniently prepared by consecutive and specific mono‐O‐demethylation, and remethylation with methyl iodide‐d₃. The sensitivity of the method is confirmed by the very low limit of detection (LOD) and quantitation (LOQ) values achieved in the assay of 1 in two distinct fortified matrices, and is further supported by the observed accuracy values. Copyright © 2009 John Wiley & Sons, Ltd.     

1H NMR metabolite fingerprinting as a new tool for body fluid identification in forensic science

In this feasibility study, we propose, for the first time, ¹H NMR spectroscopy coupled with mathematical strategies as a valid tool for body fluid (BF) trace identification in forensic science. In order to assess the ability of this approach to identify traces composed either by a single or by two different BFs, samples of blood, urine, saliva, and semen were collected from different donors, and binary mixtures were prepared. ¹H NMR analyses were carried out for all samples. Spectral data of the whole set were firstly submitted to unsupervised principal component analysis (PCA); it showed that samples of the same BF cluster well on the basis of their characterizing molecular components and that mixtures exhibit intermediate characteristics among BF typologies. Furthermore, samples were divided into a training set and a test set. An average NMR spectral profile for each typology of BF was obtained from the training set and validated as representative of each BF class. Finally, a fitting procedure, based on a system of linear equations with the four obtained average spectral profiles, was applied to the test set and the mixture samples; it showed that BFs can be unambiguously identified, even as components of a mixture. The successful use of this mathematical procedure has the advantage, in forensics, of overcoming bias due to the analyst's personal judgment. We therefore propose this combined approach as a valid, fast, and non‐destructive tool for addressing the challenges in the identification of composite traces in forensics. Copyright © 2013 John Wiley & Sons, Ltd.     

Moment based approaches to value the risk of contingent claim portfolios

In this paper we describe and apply the estimating function methodology to value the risk of asset derivative portfolios. We first implement the Li’s model based on the first four moments and then we show the limits of this model in forecasting the maximum loss of contingent claims. In addition, we show that four moments are not enough to describe the behavior of the lower percentiles of derivatives. Finally, we propose a model that considers the first six moments and we compare the performances of these models proposing a backtest analysis on several historical and truncated asset derivative portfolios.     

Mass spectrometry study of PRL‐3 phosphatase inactivation by disulfide bond formation and cysteine into glycine conversion

The Phosphatase of Regenerating Liver‐3 (PRL‐3) is a cysteine‐based phosphatase (CBP) that is highly over‐expressed in liver metastasis in colorectal cancer and suspected to be involved in the progression from tumor to metastasis. During substrate‐specificity studies based on the screening of PRL‐3 phosphatase activity on several phosphorylated synthetic peptides, we observed a decrease in activity depending on sample aging and storage conditions. By liquid chromatography combined with selective alkylation and mass spectrometry, we found two main PRL‐3 inactivation pathways: a disulfide bond formation between the catalytic C104 and C49, blocking the enzyme in an inactive oxidized form, or the conversion of the catalytic C104 into glycine. We also found that the disulfide formation and the cysteine into glycine conversion are catalyzed by cations present in the sample after protein purification through a nickel column. By adding a cation chelator such as EDTA and de‐oxygenating the sample with argon, PRL‐3 phosphatase activity was preserved. These findings suggest that PRL‐3, like other CBPs, is sensitive to inactivation by catalytic cysteine oxidation and this has implications for future studies of its activity and specificity. Copyright © 2009 John Wiley & Sons, Ltd.     

Convenient preparation of (η-alkadiene)dichloroplatinum(II) complexes from [PtCl6] anions and their reduction to platinum(0) alkene complexes under phase-transfer catalysis conditions

Convenient one-pot reduction-complexation reactions of hexachloroplatinato(IV) anions to (η⁴-alkadiene)dichloroplatinum(II) complexes (η⁴-alkadiene = COD, DAE, DCPD, NBD) under suitable phase-transfer catalysis conditions are reported. Reduction to zerovalent platinum alkene complexes has been obtained in the presence of an excess of alkene, potassium formate and 18-crown-6 as phase-transfer catalyst (alkene = COD, NB, dba). The crystal and molecular structure of [Pt_1.03(dba)₃]·CH₂Cl₂ has been studied by X-ray diffraction methods: it can be described as a solid solution of Pt(dba)₃ and Pt₂(dba)₃, the mononuclear complex being largely prevailing.     

Host–guest interactions and their role in enantioselective hydrogenation of α-keto esters: An analysis of model systems

The interaction between cinchonidine and methyl pyruvate has been proposed as the key step leading to enantiodifferentiation in the enantioselective hydrogenation of α-ketoesters. In the present work, we employ ab initio MP2/6-31G(d) and MP2/6-31G(d,p) methods to carry out an analysis of the most relevant kind of interactions operating in representative model systems. These interactions are discussed in terms of orbital superposition and dipolar interaction. When approaching H₂CO to NH₃ at distances lower than 3.4 Å, orbital superposition is the predominant interaction, while at distances above 3.4 Å, both orbital superposition and dipolar interactions may contribute to stabilization, with a small prevalence of dipolar interactions. The stabilization energy at large distances (above 4.5 Å) is very small (about 0.5 kcal mol⁻¹), probably not enough to be responsible for the enantiodifferentiation process. Semiempirical calculations on the parent systems were also unable to reveal any special interaction which could be attributed to the enantiodifferentiation process.     

A mathematical model of “Gone with the Wind”

We develop a mathematical model for mimicking the love story between Scarlett and Rhett described in “Gone with the Wind”. In line with tradition in classical physics, the model is composed of two Ordinary Differential Equations, one for Scarlett and one for Rhett, which encapsulate their main psycho-physical characteristics. The two lovers are described as so-called insecure individuals because they respond very strongly to small involvements of the partner but then attenuate their reaction when the pressure exerted by the partner becomes too high. These characteristics of Scarlett and Rhett clearly emerge during the first part of the film and are sufficient to develop a model that perfectly predicts the complex evolution and the dramatic end of the love story. Since the predicted evolution of the romantic relationship is a direct consequence of the characters of the two individuals, the agreement between the model and the film supports the high credibility of the story. Although credibility of a fictitious story is not necessary from a purely artistic point of view, in most cases it is very appreciated, at the point of being essential in making the film popular. In conclusion, we can say that we have explained with a scientific approach why “Gone with the Wind” has become one of the most successful films of all times.