Reaction of 5-hydroxy-L-tryptophan with alkyl isocyanates

5-Hydroxy-L-tryptophan 4 with potassium cyanate gives 5-(5-hydroxy-3-indolylmethyl)hydantoin 5 or N_b-carbamoyl-5-hydroxy-L-tryptophan 6 depending on the reaction conditions. Reaction of 4 with methyl iso-cyanate in acetone provides 5-hydroxy-N_b-methylcarbamoyl-L-tryptophan 7 . Treatment of 4 with ethyl, propyl and isopropyl isocyanates in acetone gives rise to the formation of the corresponding 2-[(3-alkyl-4,4-dimethyl-2-oxo)-1,3-diazetidinyl]-3-(5-hydroxy-3-indolyl)propionic acids 8–10 .     

Pore size distribution analysis of selected hexagonal mesoporous silicas by grand canonical Monte Carlo simulations

We combine here a regularization procedure with individual adsorption isotherms obtained from grand canonical Monte Carlo simulations in order to obtain reliable pore size distributions. The methodology is applied to two hexagonal high-ordered silica materials: SBA-15 and PHTS, synthesized in our laboratory. Feasible pore size distributions are calculated through an adaptable procedure of deconvolution over the adsorption integral equation, with two necessary inputs: the experimental adsorption data and individual adsorption isotherms, assuming the validity of the independent pore model. The application of the deconvolution procedure implies an adequate grid size evaluation (i.e., numbers of pores and relative pressures to be considered for the inversion, or kernel size), the fulfillment of the discret Picard condition, and the appropriate choice of the regularization parameter (L-curve criteria). Assuming cylindrical geometry for both porous materials, the same set of individual adsorption isotherms generated from molecular simulations can be used to construct the kernel to obtain the PSD of SBA-15 and PHTS. The PSD robustness is measured imposing random errors over the experimental data. Excellent agreement is found between the calculated and the experimental global adsorption isotherms for both materials. Molecular simulations provide new insights into the studied systems, pointing out the need of high-resolution isotherms to describe the presence of complementary microporosity in these materials.     

Different sites of insertion in the reaction of isocyanates with [Re(N(R)Ar)(CO)3(bipy)] (R = H or Me): N-H vs. Re-N

The reactions of isocyanates with [Re(N(R)Ar)(CO)3(bipy)] complexes lead to R'NCO insertion into the Re-N bond (for R = Me) or the N-H bond (R = H).     

Oxamato-bridged trinuclear NiIICuIINiII complexes: a new (NiIICuIINiII)2 hexanuclear complex and supramolecular structures. Characterization and magnetic properties

Eight oxamato-bridged heterotrinuclear Ni(II)Cu(II)Ni(II) complexes of formula ([Ni(H(2)O)(dpt)](2)(mu-Cu(H(2)O)(opba)))(ClO(4))2 (1), ([Ni(H(2)O)(dien)](2)(mu-Cu(pba)))(ClO(4))(2).6H(2)O (2), ([Ni(H(2)O)(Medpt)](2)(mu-Cu(OHpba)))(ClO(4))(2).4H(2)O (3), ([Ni(H(2)O)(dien)](2)(mu-Cu(Me(2)pba)))(ClO(4))(2).2.5H(2)O (4), ([Ni(H(2)O)(dpt)](2)(mu-Cu(Me(2)pba)))(ClO(4))(2).2H(2)O (5), ([Ni(H(2)O)(dien)](2)(mu-Cu(OHpba)))(ClO(4))(2).4H(2)O (6), ([Ni(2)(dpt)(2)(mu-Cu(H(2)O)(pba))](2)(mu-N(3))(2))Na(2)(ClO(4))(4).6H(2)O (7), and ([Cu(H(2)O)(2)(dpt)Ni(2)(H(2)O)(dpt)(2)](mu-H(2)Me(2)pba(2-)))(ClO(4))(4).3H(2)O (8) in which opba = o-phenylenbis(oxamato), pba = 1,3-propylenebis(oxamato), OHpba = 2-hydroxy-1,3-propylenebis(oxamato), Me(2)pba = 2,2-dimethyl-1,3-propylenbis(oxamato), dpt = 3,3'-diaminodipropylamine, dien = 2,2'-diaminodiethylamine, and Medpt = 3,3'-diamino-N-methyldipropylamine were synthesized and characterized. The crystal structures of 1, 7, and 8 were solved. For complex 1, the trinuclear entities are linked by hydrogen bonds forming a one-dimensional system, and for complex 8, the presence of van der Waals interactions gives a one-dimensional system, too. For complex 7, the trinuclear entities are self-assembled by azido ligands, given a hexanuclear system; each of these hexanuclear entities are self-assembled through two [Na(O)(3)(H(2)O)(3)] octahedral-sharing one-edge entities, given a one-dimensional system. The magnetic behavior of complexes 2-7 was investigated by variable-temperature magnetic susceptibility measurements. Complexes 2-6 exhibit the minimum characteristic of this kind of polymetallic species with an irregular spin state structure. The Jvalue through the oxamato bridge varied between -88 cm(-1) (for 6) and -111.2 cm(-1) (for 5). For complex 7, the values obtained were J(1) = -101.7 cm(-1) (through the oxamato ligand) and J(2) = -3.2 cm(-1) (through the azido ligand).     

Solid-phase extraction of soy isoflavones

An automated method using solid-phase extraction (SPE) for the concentration and clean-up of soy isoflavone extracts is proposed in this work. Using a standardized sample (0.1 g of a freeze dried soybean extract/25 mL of water); eight SPE cartridges with a wide range of sorbents (C18, divinylbenzene and modified divinylbenzene) from different suppliers were evaluated and compared. A large variation on SPE cartridges performance was observed, especially regarding retention and breakthrough volume of isoflavones during sample load and washing steps. The most effective cartridges were the divinylbenzene based cartridges, especially Strata X (from Phenomenex) and HLB oasis (from Waters). Using Strata X cartridges, several extraction parameters, such as sample loading flow (5-15 mL min(-1)), extracting solvent volume (2-6 mL of methanol), pH of the extracting solvent and the necessity of drying the sorbent before elution, were evaluated to provide a fast, specific, quantitative and reproducible SPE method. The optimized method consists of conditioning the cartridge with 10 mL of methanol and 10 mL of water (10 mL min(-1)), loading 25 mL of the standardized extract onto the cartridges (5 mL min(-1)), washing the cartridge with 10 mL of water (10 mL min(-1)) and finally eluting with 4 mL of methanol (10 mL min(-1)). Mean isoflavones recovery was 99.37% and mean intra- and inter-day reproducibility was higher than 98%. The developed sample clean-up/concentration (6.25:1) method takes less than 10 min and can be used in the analysis of isoflavones from soy extracts.     

Development of a new high performance low pressure chromatographic system using a multisyringe burette coupled to a chromatographic monolithic column

A novel combination of high performance low pressure chromatography with multisyringe flow injection analysis is presented. This system comprises a multisyringe module, three low pressure solenoid valves, a monolithic Chromolith Flash RP-18e column and a diode array spectrophotometer. UV detection is carried out at 250 nm. AutoAnalysis software is used for instrumental control and automated data collection. The results obtained with multisyringe liquid chromatography (MSC) were compared with those obtained with a HPLC system using similar conditions. The chromatographic parameters were calculated from a mixture of anthracene and thiourea using a mobile phase containing acetonitrile-water (60:40) at a flow rate of 2 ml min⁻¹. The proposed MSC system has been successfully applied to the determination of amoxicillin, ampicillin and cephalexin using a mobile phase of sodium acetate buffer (pH 6.2, 0.1 mol l⁻¹)-methanol (90:10) at a flow rate of 2 ml min⁻¹. The low-cost, flexibility and simplicity of MSC should be highlighted.     

Phase behavior and surface tensions of amphiphilic fluorinated random copolymer aqueous solutions

Phase behavior and surface tension of aqueous solutions of fluorinated random copolymers [perfluoroalkylacrylate]–[poly(ethyleneoxide)methacrylate], [C_mRf-acrylate]-[EO_n-methacrylate] with fluroalkyl carbon number m = 8, 6, 4, 2 and number of ethyleneoxide unit, n = 9 and 4.5 were investigated as a function of composition and different combinations of m and n. Isotropic solutions are formed at lower temperatures over wide concentration range of copolymer but at higher temperature phase separation occurs. The cloud point of copolymer decreases with decreasing n as well as m, and also with decreasing the number of poly(ethyleneoxide)methacrylate chain per perfluorinatedalkylacrylate chain, suggesting that the copolymers become more hydrophobic on decreasing m and n. Equilibrium and dynamic surface tension measurements show that copolymers become increasingly surface active as m as well as n decrease but the adsorption at the air–water interface is very slow due to bulkiness of the molecules. No clear evidence of the formation of micellar aggregates could be obtained from surface tension–composition curves.     

Effectiveness of universal pre-enrichment broth for recovery of Salmonella from selected dairy foods

The relative efficiencies of 2 Bacteriological Analytical Manual (BAM) pre-enrichments, lactose broth (LAC) and brilliant green water (BGW), were compared with Universal Pre-enrichment (UP) broth for the recovery of individual Salmonella serovars from instant nonfat dry milk (NFDM), dry whole milk (DWM), lactic casein (LC), and liquid whole milk (LWM). BGW was compared with UP broth for the analysis of NFDM and DWM but not with the other 2 matrixes. LAC was compared with UP broth for the analysis of LC and LWM. UP broth was made both from a commercial dehydrated preparation (UPC) and from individual ingredients (UPI). Bulk quantities of the selected dairy foods were inoculated with Salmonella serovars at levels intended to produce fractionally positive results, where at least half of the test portions analyzed, with one of the methods being evaluated, would be shown to be Salmonella-positive. For NFDM, in 6 of 9 experiments, with 2 different Salmonella serovars, BGW was significantly more productive than either UPI or UPC broth (p < 0.05). Salmonella was recovered from 118 of 180 test portions with BGW, from 25 of 180 test portions with UPC, and from 14 of 180 test portions with UPI. For DWM, in 2 of 4 experiments, with 2 different Salmonella serovars, BGW was significantly more productive than either UPI or UPC broth (p < 0.05). Salmonella was recovered from 67 of 80 test portions with BGW, from 36 of 80 test portions with UPC, and from 37 of 80 test portions with UPI. For LWM, in 9 of 9 experiments, with 3 different Salmonella serovars, there were no significant differences among the broths. Salmonella was recovered from 120 of 180 test portions with LAC, from 135 of 180 test portions with UPC, and from 129 of 180 test portions with UPI. For LC, in 5 of 7 experiments, with 2 different Salmonella serovars, both UPI and UPC broth were significantly more productive than LAC (p < 0.05). Salmonella was recovered from 42 of 140 test portions with LAC, from 114 of 140 test portions with UPC, and from 114 of 140 test portions with UPI. In addition, overall results showed that UPC and UPI broths were equivalent for the recovery of Salmonella from the foods tested, without regard to their performance in comparison with either LAC or BGW.     

Self-assembly of a hydrophobically modified naphthalene-labeled poly(acrylic acid) polyelectrolyte in water: organic solvent mixtures followed by steady-state and time-resolved fluorescence

The solution properties of two water-soluble polymers, poly(acrylic acid) (PAA), covalently labeled with the fluorescent hydrophobic dye naphthalene (Np), have been investigated in water:organic solvent mixtures. The naphthalene chromophores have been randomly attached, onto the polymer, with two different degrees of labeling. Fluorescence measurements (steady-state and time-resolved) have been used to follow the photophysical behavior of the polymers and consequently report on the self-association of the polymers in the mixed organic (methanol or dioxane):aqueous solutions. The emission spectra of the high-labeled Np PAA reveal the presence of monomer and excimer bands whereas with the low-labeled polymer only monomer emission is observed. The excitation spectra collected at the monomer and excimer emission bands show significant differences, depending on the water content of the mixture, which indicate the simultaneous presence of preformed and dynamic dimers as routes to excimer formation. The time-resolved data decay profiles of the high-labeled polymer in the mixtures were always triple exponential whereas in pure methanol and dioxane they follow biexponential laws. The data in the mixtures are consistent with two types of monomers and one excimer. Both monomers are able to give rise to excimer in the excited state, one type involving the movement of long distant Np chromophores and the other involving a local reorientation of adjacent Np chromophores. These correspond to different decay times: (1) a long which corresponds to the long distant approach of non-neighboring Np chromophores forming an excimer and (2) a short corresponding to the fast adjustment of two neighboring Np chromophores in order to have the adequate parallel geometry. An additional decay time corresponding to the excimer decay was found to be present at all wavelengths. All the decay times were dependent on the water content of the mixture. An estimation of the two excimer forming rate constants values is made for the mixed media considered in this work. On the whole, using both steady-state and time-resolved fluorescence parameters, and by comparing data for a polymer with a small number of hydrophobes with a more highly modified one, it is possible in great detail to demonstrate how association is controlled by solvent quality for the hydrophobes and by the distance between hydrophobes.