An unbreakable on-line approach towards sol-gel capillary microextraction

In this work a novel unbreakable sol-gel-based in-tube device for on-line solid phase microextraction (SPME) was developed. The inner surface of a copper tube, intended to be used as a high performance liquid chromatography (HPLC) loop, was electrodeposited by metallic Cu followed by the self assembled monolayers (SAM) of 3-(mercaptopropyl) trimethoxysilane (3MPTMOS). Then, poly (ethyleneglycol) (PEG) was chemically bonded to the -OH sites of the SAM already covering the inner surface of the copper loop using sol-gel technology. The homogeneity and the porous surface structure of the SAM and sol-gel coatings were examined using the scanning electron microscopy (SEM) and adsorption/desorption porosimetry (BET). The prepared loop was used for online in-tube SPME (capillary microextraction) of some selected polycyclic aromatic hydrocarbons (PAHs), as model compounds, from the aquatic media. After extraction, the HPLC mobile phase was used for on-line desorption and elution of the extracted analytes from the loop to the HPLC column. Major parameters affecting the extraction efficiency including the sample flow rate through the copper tube, loading time, desorption time and sample volume were optimized. For investigating the sorbent efficiency, four loops based on the copper tube itself, the copper tube after electrodeposition with Cu and the tubes with the SAMs and SAMs-sol-gel coating were made and compared. The SAMs-sol-gel coated loop clearly shows a prominently lead of at least 20-100 times of higher efficiency. The linearity for the analytes was in the range of 0.01-500 μg L(-1). Limit of detection (LOD) was in the range of 0.005-0.5 μg L(-1) and the RSD% values (n=5) were all below 8.3% at the 5 μg L(-1) level. The developed method was successfully applied to real water samples while the relative recovery percentages obtained for the spiked water samples were from 90 to 104%. The prepared loop exhibited long life time due to its remarkable solvent and mechanical stability. Different solvents such as methanol, acetonitrile and acetone were passed through the loop for many days and it was also used for more than 100 extractions/desorption of the selected analytes and no decrease in the peak areas was observed.     

Allylpalladium dimers with metals connected by binucleating dithiooxamidates in two different coordination modes: solution behavior and solid-state structure

A series of allylpalladium dimers having metals connected by binucleating dialkyldithiooxamidate [N(R)SC-CS(R)N](2-) [R = methyl, ethyl, isopropyl, benzyl, isoamyl, (S)-1-(1-phenyl)ethyl, meso-(1-phenyl)ethyl, and rac-(1-phenyl)ethyl] were prepared by reacting the monochelate [(η(3)-allyl)Pd(N(R)SC-CS(R)NH κ-S,S Pd)] with [(η(3)-allyl)PdCl](2) in chloroform. At low temperature (20 °C), the bimetallic complexes [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') (kinetic compounds) are formed in a short reaction time (10 min). At a higher temperature (50 °C) and a longer reaction time (24 h), the corresponding bimetallic isomers [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,S Pd, κ-N',S' Pd') (thermodynamic compounds) are obtained. Both kinetic and thermodynamic compounds can exist as endo or exo isomers, depending on the reciprocal orientation of the allyl cuspids. Both endo and exo isomers are only detectable in solution when the alkyl substituents are chiral alkyl groups. Moreover, diffractometric modeling agrees with the presence of both isomers in the solid state even when the alkyl substituent is an achiral alkyl group. In a chloroform solution, endo and exo isomers undergo isomeric conversion owing to the apparent allyl rotation that follows the Pd-N bond rupture in the (η(3)-allyl)Pd(N^N) frame of kinetic compounds or in the (η(3)-allyl)Pd(N^S) frame of thermodynamic compounds. The dithiooxamidate [N(R)SC-CS(R)N](2-), when engaged in a κ-N,S Pd, κ-N',S' Pd' coordination mode, behaves as a hybrid hemilabile binucleating ligand. At room temperature and in a chloroform solution, the kinetic compounds rearrange into the thermodynamically more stable isomers in about 3 or 4 days. The higher stability of the thermodynamic species was evaluated by means of computational studies in accordance with the maximum hardness principle. Finally, the crystal structures of [(η(3)-allyl)Pd](2)(μ-diethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), [(η(3)-allyl)Pd](2)(μ-meso-(1-phenyl)ethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), and [(η(3)-allyl)Pd](2)(μ-rac-(1-phenyl)ethyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') are reported.     

Raman active jagged-shaped gold-coated magnetic particles as a novel multimodal nanoprobe

The creation of novel engineered multimodal nanoparticles (NPs) is a key focus in bionanotechnology and can lead to deep understanding of biological processes at the molecular level. Here, we present a multi-component system made of gold-coupled core-shell SPIONs, as a new nanoprobe with signal enhancement in surface Raman spectroscopy, due to its jagged-shaped gold shell coating.     

Synthesis, spectral and electrochemical studies of Cu(II) and Ni(II) complexes with new N2O2 ligands: a new precursor capable of depositing copper nanoparticles using thermal reduction

Cu(II) and Ni(II) complexes of the general type [M(N2O2)] are described. The N2O2 ligands used are [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine] (HOMeSalpn) and [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,2-diamine (HOMeSalpr). These complexes have been characterized by IR, UV-vis, CV, TG-DTA and 1H NMR spectroscopy. The electrochemical behavior of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to Cu(II)-Cu(I) and Ni(II)-Ni(I) is electrochemically irreversible. The new copper complexes have been applied for the preparation of copper nanoparticles using non-ionic surfactant (Triton X-100) by thermal reduction. The copper nanoparticles with average size of 48nm were formed by thermal reduction of [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine]copper(II) in the presence of triphenylphosphine thus releasing the reduced copper and affording the high-purity copper nanoparticles.     

Enhancement of Near-Cloaking. Part II: The Helmholtz Equation

The aim of this paper is to extend the method of Ammari et al. (Commun. Math. Phys., 2012) to scattering problems. We construct very effective near-cloaking structures for the scattering problem at a fixed frequency. These new structures are, before using the transformation optics, layered structures and are designed so that their first scattering coefficients vanish. Inside the cloaking region, any target has near-zero scattering cross section for a band of frequencies. We analytically show that our new construction significantly enhances the cloaking effect for the Helmholtz equation.     

Identification of small inhomogeneities: Asymptotic factorization

We consider the boundary value problem of calculating the electrostatic potential for a homogeneous conductor containing finitely many small insulating inclusions. We give a new proof of the asymptotic expansion of the electrostatic potential in terms of the background potential, the location of the inhomogeneities and their geometry, as the size of the inhomogeneities tends to zero. Such asymptotic expansions have already been used to design direct (i.e. noniterative) reconstruction algorithms for the determination of the location of the small inclusions from electrostatic measurements on the boundary, e.g. MUSIC-type methods. Our derivation of the asymptotic formulas is based on integral equation methods. It demonstrates the strong relation between factorization methods and MUSIC-type methods for the solution of this inverse problem.

     

Solid‐particle erosion in the tube end of the tube sheet of a shell‐and‐tube heat exchanger

Erosion is one of the major problems in many industrial processes, and in particular, in heat exchangers. The effects of flow velocity and sand particle size on the rate of erosion in a typical shell‐and‐tube heat exchanger were investigated numerically using the Lagrangian particle‐tracking method. Erosion and penetration rates were obtained for sand particles of diameters ranging from 10 to 500 µm and for inlet flow velocities ranging from 0.197 to 2.95 m/s. A flow visualization experiment was conducted with the objective of verifying the accuracy of the continuous phase calculation procedure. Comparison with available experimental data of penetration rates was also conducted. These comparisons resulted in a good agreement. The results show that the location and number of eroded tubes depend mainly on the particle size and velocity magnitude at the header inlet. The rate of erosion depends exponentially on the velocity. The particle size shows negligible effect on the erosion rate at high velocity values and the large‐size particles show less erosion rates compared to the small‐size particles at low values of inlet flow velocities. The results indicated that the erosion and penetration rates are insignificant at the lower end of the velocity range. However, these rates were found to increase continuously with the increase of the inlet flow velocity for all particle sizes. The particle size creating the highest erosion rate was found to depend on the flow velocity range. Copyright © 2005 John Wiley & Sons, Ltd.     

Template Syntheses Involving the Carbon Acid Nitroethane. Synthesis and Characterization of Copper(II) Complexes of a 16-membered Tetraaza Macrocycle

New square-planar Cu(II) complexes of 3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane and 1,11-diamino-6-methyl-6-nitro-4,8-diazaundecane cations have been prepared from the one-pot template condensation of [Cu(pn)₂]²⁺ (pn=1,3-diaminopropane) in MeOH with CH₂O and EtNO₂ in the presence of a noncoordinating base. Reduction of the nitro group in the (3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane)copper(II) cation, may be achieved by Zn/acid reduction. The Cu(II) complex of the reduced form of the ligand, namely (3,11-diammonio-3,11-dimethyl-1,5,9,13-tetraazacyclohexadecane)copper(II), has also characterized. With the macrocyclic ligand, rac and meso isomers have been identified, the meso form being the major product. Elemental analyses, i.r. and u.v.–vis. spectroscopy, f.a.b. mass spectra conductometric, magnetic measurements and cyclic voltammetry have been used to characterize the complexes.     

New formulation and relaxation to solve a concave-cost network flow problem

In this paper we study a minimum cost, multicommodity network flow problem in which the total cost is piecewise linear, concave of the total flow along the arcs. Specifically, the problem can be defined as follows. Given a directed network, a set of pairs of communicating nodes and a set of available capacity ranges and their corresponding variable and fixed cost components for each arc, the problem is to select for each arc a range and identify a path for each commodity between its source and destination nodes so as to minimize the total costs. We also extend the problem to the case of piecewise nonlinear, concave cost function. New mathematical programming formulations of the problems are presented. Efficient solution procedures based on Lagrangean relaxations of the problems are developed. Extensive computational results across a variety of networks are reported. These results indicate that the solution procedures are effective for a wide range of traffic loads and different cost structures. They also show that this work represents an improvement over previous work made by other authors. This improvement is the result of the introduction of the new formulations of the problems and their relaxations.