Investigation of the dissociation pathways of metolachlor, acetochlor and alachlor under electron ionization - application to the identification of ozonation products

With the future aim of using gas chromatography coupled with mass spectrometry to characterize the transformation products of ozonated herbicides: metolachlor, acetochlor and alachlor, an interpretation of their electron ionization mass spectra is presented. Fragmentation mechanisms are proposed on the basis of isotopic labelling and multiple-stage mass spectrometry experiments carried out on an ion trap mass spectrometer. We also give examples in order to demonstrate how the elucidation of such fragmentation mechanisms for herbicides may simplify the characterization of their ozonation products.     

DBU-catalyzed transprotection of N-Fmoc-cysteine di- and tripeptides into S-Fm-cysteine di- and tripeptides

The transprotection of N-Fmoc-cysteine containing di- and tripeptides possessing a free SH group to produce the corresponding S-Fm-cysteine di- and tripeptides bearing a free amino group is accomplished efficiently with DBU in dry THF. The N-Fmoc to S-Fm transformation mechanism is discussed. S-Fm-Cysteine di- and tripeptides readily form amide bonds on coupling with N-(Pg-α-aminoacyl)benzotriazoles and N-(Pg-α-dipeptidoyl)benzotriazoles to give larger peptides.     

Urease inhibition and anti-leishmanial assay of substituted benzoylguanidines and their copper(II) complexes

A series of N,N',N'-trisubstituted guanidines (1-6) and their copper(II) complexes, [κ(2)(O,N)-C(6)H(5)CONHC(NHC(6)H(4)Cl)NR](2)Cu(ii) (R = iso-propyl (1a), n-butyl (2a), sec-butyl (3a), tert-butyl (4a), benzyl (5a), and para-tolyl (6a)) were synthesized and characterized using elemental analysis, FTIR and NMR spectroscopy. DFT studies were used to assess the location of the protons in the free ligands. However, calculations have shown that, in all cases, hydrogen bonding from either N-H group gives conformations that are very similar in energy. Single crystal XRD studies were used to characterize ligands 1 and 4 and the related complexes 1a and 4a. The structures reveal that these complexes are mononuclear in the solid state and that copper adopts a regular square planar geometry. In both metallic species, the N, N', N'-trisubstituted guanidine ligands chelate the Cu(II) atom using the oxygen and one nitrogen. The synthesized compounds were investigated for urease inhibition using thiourea as a standard drug. Most complexes exhibit a better activity than the respective guanidines and compound 1a was found to be the most active with IC(50) = 9.83 ± 0.07 μM (the IC(50) for thiourea is 21.0 ± 0.1 μM). The species were also screened for their anti-leishmanial activity. However, all of the compounds were devoid of any significant activity.     

Ring-opening metathesis polymerization-derived monolithic strong anion exchangers for the separation of 5'-phosphorylated oligodeoxythymidylic acids fragments

Ring-opening metathesis polymerization (ROMP) derived monoliths were prepared from 5-norborn-2-enemethyl bromide (NBE-CH(2)Br) and tris(5-norborn-2-enemethoxy)methylsilane ((NBE-CH(2)O)(3)SiCH(3)) within the confines of surface-silanized borosilicate columns (100 mm × 3 mm I.D.), applying Grubbs' first generation benzylidene-type catalyst [RuCl(2)(PCy(3))(2)(CHPh)]. Two monoliths of the same recipe were converted into strong anion-exchangers applying two different approaches. Monolith I was prepared by a two-step reaction of the poly(NBE-CH(2)-Br) moieties with diethyl amine forming a weak-anion exchanger followed by reaction (quaternization) with ethyl iodide. Monolith II was prepared via a single-step reaction of the poly(NBE-CH(2)-Br) moieties with triethyl amine. The resulting monolithic anion-exchangers prepared demonstrated a good aptitude for the anion-exchange separation of single-stranded nucleic acids (ss-DNA). However, monolith II showed superior separation efficiency compared to monolith I indicated by sharper analyte peaks and better resolution values for the 5'-phosphorylated oligodeoxythymidylic acids fragments. On monolith II, the seven fragments of [d(pT)(12-18)] were baseline separated in less than 9 min. The influence of the buffer pH on the separation efficiency was studied applying a phosphate (0.05 mol/L, pH 7 and 8) and Tris-HCl buffer (0.05 mol/L, pH 9), respectively.     

In vitro cytotoxic evaluation of some new heterocyclic sulfonamide derivatives

Sulfonamide‐bearing compounds posses many types of biological activities and have been recently reported to show substantial antitumor activity in vitro and/or in vivo. There are a variety of mechanisms for the anticancer activity, and the most prominent mechanism is the inhibition of carbonic anhydrase isozymes. This work reports the synthesis of some new quinoline, pyrimido[4,5‐b]quinoline and 3,1‐oxazinoquinoline derivatives bearing a sulfonamide moiety. All the newly synthesized compounds were evaluated for their in vitro anticancer activity against Ehrlich ascites carcinoma cells. Compounds 10 , 13 , and 26 were the most active compounds with IC₅₀ values of 6.1 μM, 6.8 μM, and 6.4 μM, respectively, and exhibited better activities than the reference drug doxorubicin (IC₅₀ = 68.1 μM). J. Heterocyclic Chem., 2011.     

Regularity of Nash payoffs of Markovian nonzero-sum stochastic differential games

In this paper we deal with the problem of existence of a smooth solution of the Hamilton–Jacobi–Bellman–Isaacs (HJBI for short) system of equations associated with nonzero-sum stochastic differential games. We consider the problem in unbounded domains either in the case of continuous generators or for discontinuous ones. In each case we show the existence of a smooth solution of the system. As a consequence, we show that the game has smooth Nash payoffs which are given by means of the solution of the HJBI system and the stochastic process which governs the dynamic of the controlled system.     

Silver compounds in synthetic chemistry. Part 3. 4-Tetrafluoropyridyl silver(I), AgC5F4N - A reagent for redox transmetallations with group 12-14 elements

4-Tetrafluoropyridyl silver(I), AgC₅F₄N, has been obtained from Me₃SiC₅F₄N and AgF in nearly quantitative yield. Reactions with bis(triphenylphosphoranyliden)ammonium chloride, [PNP]Cl, gave crystalline material of the composition [PNP][Ag(C₅F₄N)₂]. Redox transmetallations of AgC₅F₄N and group 12-14 elements Zn, Cd, Hg, Ga, In, Sn yielded the corresponding 4-tetrafluoropyridyl element compounds. The molecular structures of [PNP][Ag(C₅F₄N)₂], Hg(C₅F₄N)₂, Ga(C₅F₄N)₃ · EtCN · H₂O, In(C₅F₄N)₃ · 2EtCN and Sn(C₅F₄N)₄ are discussed.     

A nonlinear nonlocal mixed problem for a second order pseudoparabolic equation

We study a nonlocal mixed problem for a nonlinear pseudoparabolic equation, which can, for example, model the heat conduction involving a certain thermodynamic temperature and a conductive temperature. We prove the existence, uniqueness and continuous dependence of a strong solution of the posed problem. We first establish for the associated linear problem a priori estimate and prove that the range of the operator generated by the considered problem is dense. The technique of deriving the a priori estimate is based on constructing a suitable multiplicator. From the resulted energy estimate, it is possible to establish the solvability of the linear problem. Then, by applying an iterative process based on the obtained results for the linear problem, we establish the existence, uniqueness and continuous dependence of the weak solution of the nonlinear 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.