Analysis of drugs of forensic interest with capillary zone electrophoresis/time-of-flight mass spectrometry based on the use of non-volatile buffers

The present work is aimed at investigating the influence of the background electrolyte composition and concentration on the separation efficiency and resolution and mass spectrometric detection of illicit drugs in a capillary zone electrophoresis-electrospray ionization-time of flight mass spectrometry (CZE-ESI-TOF MS) system. The effect of phosphate, borate and Tris buffers on the separation and mass spectrometry response of a mixture of 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, methadone, cocaine, morphine, codeine and 6-monoacetylmorphine was studied, in comparison with a reference ammonium formate separation buffer. Inorganic non-volatile borate and Tris buffers proved hardly suitable for capillary electrophoresis-mass spectrometry (CE-MS) analysis, but quite unexpectedly ammonium phosphate buffers showed good separation and ionization performances for all the analytes tested. Applications of this method to real samples of hair from drug addicts are also provided.     

Epoxidation of olefins with a silica-supported peracid in supercritical carbon dioxide under flow conditions

Anhydrous 2-percarboxyethyl-functionalized silica (2b), a recyclable supported peracid, is a suitable reagent to perform the epoxidation of alkenes 1 in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions. This procedure simplifies the isolation of the reaction products and uses only carbon dioxide as a solvent under mild conditions. The solid reagent 2b can be easily recycled by a reaction with 30% hydrogen peroxide in an acid medium.     

The Coordination of Ni(II) and Cu(II) Ions to the Polyhistidyl Motif of Hpn Protein: Is It as Strong as We Think?

Hpn, one of Helicobacter pylori's nickel-accessory proteins, is an amazingly peculiar protein: Almost half of its sequence consists of polyhistidyl (poly-His) residues. Herein, we try to understand the origin of this naturally occurring sequence, thereby shedding some light on the bioinorganic chemistry of Hpn's numerous poly-His repeats. By using potentiometric, mass spectrometric, and various spectroscopic techniques, we studied the Ni(II) - and Cu(II) complexes of the wild-type Ac-THHHHYHGG-NH(2) fragment of Hpn and of its six analogues, in which consecutive residues (His or Tyr) were replaced by Ala (Ala-substitution or Ala-scan approaches), thereby resulting in Ac-TAHHHYHGG-NH(2) , Ac-THAHHYHGG-NH(2) , Ac-THHAHYHGG-NH(2) , Ac-THHHAYHGG-NH(2) , Ac-THHHHAHGG-NH(2) , and Ac-THHHHYAGG-NH(2) peptides. We found that the His4 residue is critical for both Ni(II) - and Cu(II) -ion binding and the effectiveness of binding varies even if the substituted amino acid does not take part in the direct binding interactions.     

p-Laplacian problems with nonlinearities interacting with the spectrum

The aim of this paper is investigating the existence and the multiplicity of weak solutions of the quasilinear elliptic problem $$\left\{\begin{array}{ll}-\Delta_p u\ =\ g(x, u) \quad {\rm in} \quad \Omega,\\ u=0 \qquad \qquad \qquad {\rm on}\quad \partial\Omega,\end{array}\right.$$ where ${1 < p < + \infty, \Delta_p u = {\rm div}(|\nabla {u}|^{p-2}\nabla {u})}$ , Ω is an open bounded domain of ${\mathbb{R}^N (N \geq 3)}$ with smooth boundary ?Ω and the nonlinearity g behaves as u ^p?1 at infinity. The main tools of the proof are some abstract critical point theorems in Bartolo et al. (Nonlinear Anal. 7: 981–1012, 1983), but extended to Banach spaces, and two sequences of quasi–eigenvalues for the p–Laplacian operator as in Candela and Palmieri (Calc. Var. 34: 495–530, 2009), Li and Zhou (J. Lond. Math. Soc. 65: 123–138, 2002).     

A comprehensive mathematical approach to exotic option pricing

This work illustrates how several new pricing expressions for exotic options can be derived within a Lévy framework by employing a unique pricing expression. To the purpose, a unifying formula is obtained by solving some nested Cauchy problem for pseudodifferential equations generalizing Black–Scholes PDE. The main result extends (Agliardi R. The quintessential option pricing formula under Lévy processes. Applied Mathematics Letters 2009; 22:1626‐1631) and is a powerful tool for generating new valuation expressions. Several examples of pricing formulas under the Lévy processes are provided to illustrate the flexibility of the method. Some of them are new in the financial literature. Finally, many existing pricing formulas of the traditional Gaussian model are easily obtained as a by‐product. Copyright © 2012 John Wiley & Sons, Ltd.     

On the inter-instrument and the inter-laboratory transferability of a tandem mass spectral reference library. 3. Focus on ion trap and upfront CID

Mass spectral libraries represent versatile tools for the identification of small bioorganic molecules. Libraries based on electron impact spectra are rated robust and transferable. Tandem mass spectral libraries are often considered to work properly only on the instrument that has been used to build the library. An exception from that rule is the 'Wiley Registry of Tandem Mass Spectral Data, MSforID'. In various studies with data sets from different kinds of tandem mass spectrometric instruments, the outstanding sensitivity and robustness of this tandem mass spectral library search approach was demonstrated. The instrumental platforms tested, however, mainly included various tandem-in-space instruments. Herein, the results of a multicenter study with a focus on upfront and tandem-in-time fragmentation are presented. Five laboratories participated and provided fragment ion mass spectra from the following types of mass spectrometers: time-of-flight (TOF), quadrupole-hexapole-TOF, linear ion trap (LIT), 3-D ion trap and LIT-Orbitrap. A total number of 1231 fragment ion mass spectra were collected from 20 test compounds (amiloride, buphenin, cinchocaine, cyclizine, desipramine, dihydroergotamine, dyxirazine, dosulepin, ergotamine, ethambutol, etofylline, mefruside, metoclopramide, phenazone, phentermine, phenytoin, sulfamethoxazole, sulfamoxole, sulthiame and tetracycline) on seven electrospray ionization instruments using 18 different instrumental configurations for fragmentation. For 1222 spectra (99.3%), the correct compound was retrieved as the best matching compound. Classified matches (matches with 'relative average match probability' >40.0) were obtained for 1207 spectra (98.1%). This high percentage of correct identifications clearly supports the hypothesis that the tandem mass spectral library approach tested is a robust and universal identification tool.     

The quintessential option pricing formula under Lévy processes

The basic digital method for option pricing developed in Ingersoll [J. Ingersoll, Digital contracts: Simple tools for pricing complex derivatives, Journal of Business 73 (1) (2000) 67–88] and Buchen and Skipper [P. Buchen, M. Skipper, The quintessential option pricing formula, School of Mathematics and Statistics, University of Sydney, 2003, pp. 1–31] is generalized to a Lévy environment. The approach is combined with the mathematical methodology of Boyarchenko and Levendorski [S.I. Boyarchenko, S.Z. Levendorski, Non-Gaussian Merton–Black–Scholes theory, World Scientific, 2002] that employs pseudo-differential operators whose symbol is expressed in terms of the characteristic exponent of the underlying Lévy process. Some new valuation formulas are obtained.     

Unusually high enantioselectivity in high-performance liquid chromatography using cellulose tris(4-methylbenzoate) as a chiral stationary phase

The cellulose tris(4-methylbenzoate) chiral stationary phase (CSP) (commercially known as Chiralcel OJ-H) exhibited an extremely high enantioselectivity when used in the HPLC resolution of N-thiocarbamoyl-3-(4′-prenyloxy)-phenyl-5-phenyl-4,5-dihydro-(1H) pyrazole (Compound 1), in both normal-phase and polar organic conditions. Using n-hexane–ethanol (80:20, v/v) as a mobile phase, an enantioseparation factor value of 138.5 was found. In order to modulate the elution time of the longer retained enantiomer, a simple HPLC procedure was developed. The optimized analytical protocol was based on the stopped flow technique and did not involve any change in mobile phase composition. The stronger interaction energy of the (S) enantiomer compared to that of the (R) enantiomer was mainly attributed to the formation of a hydrogen bonding between the amino group of the thiocarbamoyl moiety and the carbonyl oxygen of the CSP.     

Selection of Anti‐gluten DNA Aptamers in a Deep Eutectic Solvent

Herein, we show the feasibility of using deep eutectic solvents as a faster way of selecting aptamers targeting poorly water‐soluble species. This unexplored concept is illustrated for gluten proteins. In this way, aptamer‐based gluten detection can be performed directly in the extraction media with improved detectability. We envision deep implications for applications not only in food safety control but also in biomedicine.