Capillary electrochromatography–mass spectrometry determination of melamine and related triazine by-products using poly(divinyl benzene-alkene-vinylbenzyl trimethylammonium chloride) monolithic stationary phases

In this study, a capillary electrochromatography (CEC) method coupled either with UV or mass spectrometric detection was developed for the detection of trace-amounts of melamine and its related by-products (ammeline, ammelide, and cyanuric acid). A series of poly(divinyl benzene-alkene-vinylbenzyl trimethylammonium chloride) monolithic columns, which were prepared by a simple in situ polymerization with divinyl benzene (DVB), vinylbenzyl trimethylammonium chloride (VBTA) and different types of alkene monomers such as 1-octene, 1-dodecene or 1-octadecene were used as separation columns, with the poly(DVB-1-dodecene-VBTA) monolith as the optimal chromatographic material because it provided a better separation. The detection limits of four melamine derivatives were in the ranged of 0.6–2.18 mg L⁻¹ by the optimal CEC–UV mode, and were reduced from 2.2 to 19.4 μg L⁻¹ by the optimal CEC–MS mode. Finally, the proposed CEC methods successfully determined melamine contaminations (0.1 mg L⁻¹ per analyte) in several dairy products as test samples with analyte recovery range of 69–85% (intra-day) and 68–75% (inter-day), and with peak area reproducibility range of 4.3–8.6% and 8.7–15.6% for intra-day and inter-day, respectively. This is the first report for CEC separation coupled with MS detection applied in trace melamine residue analyses with a faster separation and comparable or even better detection ability than previous GC–MS, CE–MS, as well as LC–MS methods.     

A practical, metal-free synthesis of 1H-indazoles

The synthesis of 1H-indazoles is achieved from o-aminobenzoximes by the selective activation of the oxime in the presence of the amino group. The reaction occurs with a variety of substituted o-aminobenzoximes using a slight excess of methanesulfonyl chloride and triethylamine at 0-23 degrees C and is amenable to scale-up. The synthesis of 1H-indazoles under these conditions is extremely mild compared with previous synthetic approaches and affords the desired compounds in good to excellent yields.     

A trinuclear heterobimetallic Ru(II)/Pt(II) complex as a chemodosimeter selective for sulfhydryl-containing amino acids and peptides

A trinuclear heterobimetallic Ru(II)/Pt(II) complex, cis-{Ru(phen)2[CN-Pt(DMSO)Cl2]2} (phen = 1,10-phenanthroline), is able to function as a "switch-on" luminescent chemodosimeter for sulfhydryl-containing amino acids and peptides via specific binding of the amino acids/peptides with the Pt(II) centers and the subsequent cleavage of the Ru(II)-Pt(II) cyano-bridge.     

A memetic algorithm for the multiperiod vehicle routing problem with profit

In this paper, we extend upon current research in the vehicle routing problem whereby labour regulations affect planning horizons, and therefore, profitability. We call this extension the multiperiod vehicle routing problem with profit (mVRPP). The goal is to determine routes for a set of vehicles that maximizes profitability from visited locations, based on the conditions that vehicles can only travel during stipulated working hours within each period in a given planning horizon and that the vehicles are only required to return to the depot at the end of the last period. We propose an effective memetic algorithm with a giant-tour representation to solve the mVRPP. To efficiently evaluate a chromosome, we develop a greedy procedure to partition a given giant-tour into individual routes, and prove that the resultant partition is optimal. We evaluate the effectiveness of our memetic algorithm with extensive experiments based on a set of modified benchmark instances. The results indicate that our approach generates high-quality solutions that are reasonably close to the best known solutions or proven optima, and significantly better than the solutions obtained using heuristics employed by professional schedulers.     

The millimeter wave rotational spectrum of N-cyanomethanimine,CH2NCN

The rotational spectrum of the short-lived species N-cyanomethanimine, CH₂NCN, has been measured in the frequency range 100–250 GHz. The observed transitions allow the determination of the rotational and centrifugal distortion constants and the nitrogen quadrupole coupling constants for both nitrogen nuclei. The N-cyanomethanimine spectrum was measured directly in the products of the pyrolysis of trimethylenetetrazole. The rotational constants obtained are A = 63 372.995(11) MHz, B = 5 449.347 90(28) MHz, and C = 5 009.559 86(29) MHz; the quadrupole coupling constants are χ_aa = 2.057(39) MHz and χ_bb ? χ_cc = ?7.205(21) MHz for the imine nitrogen, and χ_aa = ?3.264(33) MHz and χ_bb ? χ_cc = ?1.630(18) MHz for the cyano-group nitrogen. The accurate constants obtained allow the calculation of the line position and hyperfine structure of any rotational transition appropriate for a radioastronomical search.     

New method for sintering silica frits for capillary microcolumns

One of the main steps in the manufacture of robust and efficient packed capillary microcolumns for electro- and capillary chromatography is the generation of porous devices to retain the packed beds. Frits based on sintered silica particles have been found to give the best results in terms of mechanical resistance and efficiency. The conventional procedure to produce these kinds of frits consists in a radial heating of the packed material with either a flame or an electrical resistance, but the frits thus obtained have many drawbacks as a result of the procedure rather than the silica per se as the base material. In the present work we investigated a new approach to produce silica-based retaining devices involving the frontal exposure of a short silica-particle bed packed at the end of a capillary tube. The capillary is radially insulated and frontally exposed to the heat of a muffle oven, generating a transfer of heat that is not radial but rather throughout the capillary axis. This procedure resulted in substantial advantages: an improved radial homogeneity, a protection of the external polyimide, and a generation of extremely short (400–600 μm) frits that were highly permeable and avoided bubble formation.     

Analyses of sulfonamide antibiotics in meat samples by on-line concentration capillary electrochromatography-mass spectrometry

In this work, a series of poly(divinylbenzene-alkyl methacrylate) monolithic stationary phases, which were prepared by single step in situ polymerization of divinylbenzene and various alkyl methacrylates (butyl-, octyl-, lauryl- or stearyl methacrylate), were developed as separation columns of nine common sulfonamide antibiotics for capillary electrochromatography (CEC) coupled to mass spectrometry (MS). Results indicated that the sulfonamide's retention became weak with increased carbon chain length of alkyl methacrylate monomer (for example, t(R)=68 min and 21 min for butyl- and lauryl methacrylate, respectively). Among them, the poly(divinylbenzene-octyl methacrylate) (poly(DVB-OMA)) monolith was regarded as the optimal separation column as this provided better resolution within the shortest retention time. Moreover, the cross-sectional roughness of the monolithic column-end, that was used to couple to the ESI interface, strongly influenced the electrospray stability in the CEC-MS. Before the column was connected to the ESI-MS, a simple polishing was done to reduce the roughness of the column end that resulted to a great improvement in the signal stability. The relative standard deviations (RSDs) of the peak areas for the unpolished and polished ends of the poly(DVB-OMA) columns (n=5) were in the range of 46.1-60.2% and 8.9-16.4%, respectively. Furthermore, optimization of the mobile phase composition and the gradient elution strategy successfully determined the sulfonamide antibiotics in meat samples with as low as 10 μg/L level.     

Practical syntheses of a CXCR3 antagonist

Two new, reliable syntheses of a pyrido[2,3-d]-pyrimidine inhibitor of the CXCR3 receptor are described. A nine-step synthesis of the CXCR3 inhibitor (1) from 2-aminonicotinic acid was demonstrated on a multikilogram scale and incorporates a classic resolution to deliver the enantioenriched active pharmaceutical ingredient (API). A second synthesis of the CXCR3 inhibitor starts from (+)-(D)-Boc alanine and 2-chloronicotinic acid and utilizes a Goldberg coupling. This second synthesis, performed on a gram scale, intersects the former route at a common intermediate thereby completing a formal synthesis of the enantioenriched API in higher overall yield without the need for a resolution.     

Solid state structure and absolute configuration of filifolinol acetate

Careful reevaluation of the 1H and 13C NMR spectroscopic data of filifolinol acetate (4) led to the reassignment of the C-10 and C-11 signals, as well as the gem-dimethyl signals. Single crystal X-ray analysis provided an independent structural confirmation of 4, and comparison of the experimental vibrational circular dichroism spectrum with calculations performed using density functional theory provided the absolute configuration of this 3H-spiro-1-benzofuran-2,1'-cyclohexane and related molecules.