Ultra-performance liquid chromatography for the determination of pesticide residues in foods by tandem quadrupole mass spectrometry with polarity switching

An ultra-performance liquid chromatographic (UPLC) electrospray ionisation tandem quadrupole mass spectrometric method has been developed for the determination of 52 pesticides in cereal-based baby foods, oranges and potatoes. The fast polarity switching capability of the mass spectrometer used enabled the determination of 44 of the compounds in the positive ionisation mode and 8 of the compounds in the negative ionisation mode in a single run. Prior to analysis, co-extractives were removed from acetonitrile extracts using dispersive solid-phase extraction with primary secondary amine (50 mg). The UPLC method separates all of the pesticides, resolves structural isomers (e.g. butocarboxim sulfoxide and aldicarb sulfoxide) and has a short (7 min) cycle time. Extracts spiked with pesticides at 0.10 and 0.01 mg kg(-1) yielded average recoveries in the range of 66-124% with relative standard deviations less than 19% for the majority of the analytes.     

Synthesis of novel polyaryl(ether–ketones) with tert-butyl pendent groups

Linear polyaryl(ether ketones) containing tert-butyl pendent groups were prepared from aromatic hydrocarbons and aromatic diacid chlorides, both classes of monomers containing tert-butyl pendent groups. The polymers were prepared in high yield and high molecular weight by low-temperature precipitation polycondensation in 1,2-dichloroethane. The presence of meta-oriented moieties and bulky pendent groups played a beneficial role with regard to solubility, while the thermal transitions and thermal resistance were not greatly impaired relative to conventional all para-oriented polyaryl(ether–ketones). The current polyaryl(ether–ketones) showed glass transition temperatures in the range 170–240°C and decomposition temperatures, as measured by TGA, of about 500°C. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1251–1256, 1998     

Dielectric relaxation of LC-thermotropic poly(ester imide)s

Two different series of poly(ester imide)s, which are distinguished from each other in the orientation of the ester linkages and show well-differentiated thermotropic behavior, are investigated by means of model calculations and dielectric relaxation spectroscopy. Model calculations show that the orientation of the ester linkages has a strong influence on the rotational energy barriers. The dielectric relaxation spectra of both series shows three relaxation regions in the temperature range between 100 and 400 K that have been identified as the α-, β- and γ-relaxation processes. A difference of about two orders of magnitude between the characteristic rates of the γ-relaxation is the main feature observed in the dielectric response. However, the β-relaxation shows very similar behavior for both series. The differences in the relaxation behavior in the solid state are interpreted on the basis of the rotational barriers deduced from the model calculation results. © 1997 John Wiley & Sons, Inc.     

Three-step approach for prediction of limit cycle pressure oscillations in combustion chambers of gas turbines

Currently, gas turbine manufacturers frequently face the problem of strong acoustic combustion driven oscillations inside combustion chambers. These combustion instabilities can cause extensive wear and sometimes even catastrophic damages to combustion hardware. This requires prevention of combustion instabilities, which, in turn, requires reliable and fast predictive tools. This work presents a three-step method to find stability margins within which gas turbines can be operated without going into self-excited pressure oscillations. As a first step, a set of unsteady Reynolds-averaged Navier–Stokes simulations with the Flame Speed Closure (FSC) model implemented in the OpenFOAM® environment are performed to obtain the flame describing function of the combustor set-up. The standard FSC model is extended in this work to take into account the combined effect of strain and heat losses on the flame. As a second step, a linear three-time-lag-distributed model for a perfectly premixed swirl-stabilized flame is extended to the nonlinear regime. The factors causing changes in the model parameters when applying high-amplitude velocity perturbations are analysed. As a third step, time-domain simulations employing a low-order network model implemented in Simulink® are performed. In this work, the proposed method is applied to a laboratory test rig. The proposed method permits not only the unsteady frequencies of acoustic oscillations to be computed, but the amplitudes of such oscillations as well. Knowing the amplitudes of unstable pressure oscillations, it is possible to determine how these oscillations are harmful to the combustor equipment. The proposed method has a low cost because it does not require any license for computational fluid dynamics software.     

Statistical mechanics and dynamics of solvable models with long-range interactions

For systems with long-range interactions, the two-body potential decays at large distances as V(r)1/r^α, with α≤d, where d is the space dimension. Examples are: gravitational systems, two-dimensional hydrodynamics, two-dimensional elasticity, charged and dipolar systems. Although such systems can be made extensive, they are intrinsically non additive: the sum of the energies of macroscopic subsystems is not equal to the energy of the whole system. Moreover, the space of accessible macroscopic thermodynamic parameters might be non convex. The violation of these two basic properties of the thermodynamics of short-range systems is at the origin of ensemble inequivalence. In turn, this inequivalence implies that specific heat can be negative in the microcanonical ensemble, and temperature jumps can appear at microcanonical first order phase transitions. The lack of convexity allows us to easily spot regions of parameter space where ergodicity may be broken. Historically, negative specific heat had been found for gravitational systems and was thought to be a specific property of a system for which the existence of standard equilibrium statistical mechanics itself was doubted. Realizing that such properties may be present for a wider class of systems has renewed the interest in long-range interactions. Here, we present a comprehensive review of the recent advances on the statistical mechanics and out-of-equilibrium dynamics of solvable systems with long-range interactions. The core of the review consists in the detailed presentation of the concept of ensemble inequivalence, as exemplified by the exact solution, in the microcanonical and canonical ensembles, of mean-field type models. Remarkably, the entropy of all these models can be obtained using the method of large deviations. Long-range interacting systems display an extremely slow relaxation towards thermodynamic equilibrium and, what is more striking, the convergence towards quasi-stationary states. The understanding of such unusual relaxation process is obtained by the introduction of an appropriate kinetic theory based on the Vlasov equation. A statistical approach, founded on a variational principle introduced by Lynden-Bell, is shown to explain qualitatively and quantitatively some features of quasi-stationary states. Generalizations to models with both short and long-range interactions, and to models with weakly decaying interactions, show the robustness of the effects obtained for mean-field models.     

Extensions and biextensions of locally constant group schemes,tori and abelian schemes

Let S be a scheme. We compute explicitly the group of homomorphisms, the S-sheaf of homomorphisms, the group of extensions, and the S-sheaf of extensions involving locally constant S-group schemes, abelian S-schemes, and S-tori. Using the obtained results, we study the categories of biextensions involving these geometrical objects. In particular, we prove that if G _i (for i = 1, 2, 3) is an extension of an abelian S-scheme A _i by an S-torus T _i , the category of biextensions of (G ₁, G ₂) by G ₃ is equivalent to the category of biextensions of the underlying abelian S-schemes (A ₁, A ₂) by the underlying S-torus T ₃.      

Energy transfer in hybrids based on a thiophene-substituted ethynylbipyridine dimer decorated with Re(I), Ru(II), and Os(II) units

The preparation, structural features, electrochemical behavior, and optical properties (at room temperature and at 77 K) are reported for a series of thiophene-containing hybrids based on the bent conjugated backbone of a rigid ditopic ligand, the dimeric moiety 3,4-dibutyl-2,5-bis{5'-[(3,4-dibutylthien-2-ylethynyl)-2,2'-bipyridin-5-yl]ethynyl}thiophene (TBTBT). Within the dimer, the diethynyl-2,2'-bipyridine units (bpy, the coordination sites) alternate with three 3,4-dibuthylthiophene units and coordination of the [Re(CO)3Cl], [Ru(bpy)2]2+, and [Os(bpy)2]2+ centers results in the mononuclear species RuTBTBT and OsTBTBT and the binuclear species RuTBTBTRu, OsTBTBTOs, RuTBTBTOs, and ReTBTBTOs. At room temperature, the emitting states obtained by photoexcitation are of 3MLCT nature, and vibronic analysis of the emission spectra indicates that they are largely delocalized over the TBTBT ligand. In the binuclear species, the intermetal separation is ca. 17 A, and for RuTBTBTOs, an efficient Ru --> Os excitation transfer takes place, resulting solely in an Os-based emission. The process is ascribed to double-electron transfer (Dexter), as mediated by the TBTBT ligand; a similar conclusion holds for the case of ReTBTBTOs. For RuTBTBTOs, the process is discussed in some detail also with regard to the possibility of disentangling the constituent hole and electron-transfer events.     

Overview on advances in capillary electrophoresis-mass spectrometry of carbohydrates: a tabulated review

The increasing interest for carbohydrates as holder of essential bioinformations has boosted their full characterization through analytical techniques. The intent of this review is to summarize the recent trends regarding on-line and off-line CE-MS coupling for carbohydrate analysis. A statistical survey on the articles that use derivatizing agents as well as on the analyzer and type of instrument coupling (i.e. on- or off-line) is depicted. From a general overview it can be concluded that, whereas derivatization might be useful for the detection of neutral carbohydrates improving separation selectivity with volatile buffers and increasing sensitivity of the MS detection, relatively few works with derivatized carbohydrates were found; this was noticed in particular for glycosides and saccharides carrying ionizable groups, which are normally analyzed without any chemical modification. The most applied coupling is the on-line sheath-liquid interface; for on-line applications, ESI is the sole source used, whilst the most common analyzer is the IT. MS(n) is often exploited, as fragmentation increases the achieved structural information. CE-MS turned out to be mainly used for the analysis of carbohydrates in drug development (i.e. study of oligosaccharides from pathogens, carbohydrate-based drugs and drug metabolites), in nutrition and for characterization of glycans from glycoproteins. The reader will find elucidating tables regarding these recent CE-MS applications, including the main information on the analysis conditions. Comments are meant to help the immediate focus on the usefulness of the analytical technique and predict the difficulties found during analysis and, in case, their overcoming.     

Enantioselective multicomponent synthesis of fused 6-5 bicyclic 2-butenolides by a cascade heterobicyclisation process

The successive coupling of an alkoxy(aryl/heteroaryl)carbene complex of chromium with either a ketone or an imide lithium enolate and then a 3-substituted (H, TMS, PhCH(2), PhCH(2)CH(2), Me) propargylic organomagnesium reagent has afforded novel hydroxy-substituted bicyclic [4.3.0]-γ-alkylidene-2-butenolides with three modular points that has allowed the efficient introduction of molecular complexity, including a homopropargylic alcohol core. The selective formation of these five- or six-component heterobicyclisation products is the result of the regioselective integration of the Grignard reagent as a propargyl fragment followed by a cascade CO/alkyne/CO insertion, ketene trapping and elimination sequence. By using lithium enolates of chiral N-acetyl-2-oxazolidinones and the corresponding propargylic organocerium reagents, both enantiomers of these bicyclic heterocycles were efficiently prepared with very high enantiomeric purity. Architecturally, these fused bicyclic butenolides are characterised by a highly unsaturated and oxygenated core and they exhibit strong blue fluorescence in solution.     

Synthesis and Properties of Novel Polyimides Bearing Sulfonated Benzimidazole Pendant Groups

A new diamine monomer containing benzimidazole‐5‐sulfonic acid has been synthesised. It has been reacted, alone or mixed with diaminodiphenyl ether, with naphthalenic dianhydride to attain polynaphthalimides in which the sulfonic acid functionality is borne by pendant benzimidazole groups. The presence of sulfonic and benzimidazole groups greatly affected the physical properties of the polyimides as the novel polymers were found to be soluble in polar organic solvents and exhibited a lower thermal resistance than their non‐sulfonated counterparts. The polymer films exhibited good mechanical properties with tensile strength in the range 100–120 MPa and with moduli in the range 2.2–3.1 GPa. Sulfonic and benzimidazole groups significantly enhanced the hydrophilicity of the copolyimides, which showed water uptake up to 39%.