A Six-Vertex Theorem for Bounding Normal Planar Curves

We prove that the number of vertices of a smooth normal planarcurve is at least 6, if it bounds a surface other than the disk.     

Models for copper proteins. Copper(I) and (II) complexes of a novel binucleating tetraamino-tetrathioether ligand

The novel binucleating ligand, 6,6 prime-methylene-bis(5 prime-amino-3 prime,4 prime-benzo-2 prime-thiapentyl)-1,11-diamino-2,3:9,10-dibenzo-4,8-dithiaundecane (H4L) was prepared and reacted with copper(II) salts in dry MeOH to yield mixtures of copper(I) and copper(II) complexes with Cl- and ClO-4 counter ions. The amine functions on the ligand release protons to form copper(I) complexes: (Cu2L)X2, where X=Cl−, ClO4-. The complexes were oxidized to (Cu2L)X4 with H2O2 in DMF; Cu(NO3)2 gave a different complex, [Cu2(H4L)(NO3)2](NO3)2, as regards proton releasing ability, coordination and oxidation number. Evidence for the structures of this new tetraamino-tetrathioether ligand and its copper complexes is provided by 1H-, 13C-n.m.r., mass, u.v.–vis., i.r. spectra, elemental analyses, molar conductivities and magnetic moments. This revised version was published online in June 2006 with corrections to the Cover Date.     

Determination of thiamine HCl and pyridoxine HCl in pharmaceutical preparations using UV-visible spectrophotometry and genetic algorithm based multivariate calibration methods

Simultaneous determination of binary mixtures pyridoxine hydrochloride and thiamine hydrochloride in a vitamin combination using UV-visible spectrophotometry and classical least squares (CLS) and three newly developed genetic algorithm (GA) based multivariate calibration methods was demonstrated. The three genetic multivariate calibration methods are Genetic Classical Least Squares (GCLS), Genetic Inverse Least Squares (GILS) and Genetic Regression (GR). The sample data set contains the UV-visible spectra of 30 synthetic mixtures (8 to 40 microg/ml) of these vitamins and 10 tablets containing 250 mg from each vitamin. The spectra cover the range from 200 to 330 nm in 0.1 nm intervals. Several calibration models were built with the four methods for the two components. Overall, the standard error of calibration (SEC) and the standard error of prediction (SEP) for the synthetic data were in the range of <0.01 and 0.43 microg/ml for all the four methods. The SEP values for the tablets were in the range of 2.91 and 11.51 mg/tablets. A comparison of genetic algorithm selected wavelengths for each component using GR method was also included.     

Synthesis of 5,6-O-Cyclohexylidene-1-amino-3-azahexane and Its Co(II), Ni(II), Cu(II) Complexes

5,6-O-Cyclohexylidene-1-amino-3-azahexane (L) is synthesized from 1-chloro-2,3-O-cyclohexylidenepropane, which is prepared by the reaction between epichlorohydrin and cyclohexanone. In this reaction, BF₃ · OEt₂ is used as a catalyst. Complexes of Co(II), Ni(II) and Cu(II) acetates with this ligand are prepared. The structures of the ligand and its complexes are proposed based on elemental analysis, IR and UV-VIS spectroscopy, magnetic susceptibility, conductometry, and ¹H and ¹³C NMR spectroscopy.     

Effect of electrolytes on the surface behavior of rhamnolipids R1 and R2

The surface behavior of solutions of the rhamnolipids, R1 and R2, were investigated in the absence and presence of an electrolyte (NaCl) through surface tension measurements and optical microscopy at pH 6.8. The NaCl concentrations studied are 0.05, 0.5 and 1 M. Electrolytes directly affect the carboxylate groups of the rhamnolipids. The solution/air interface has a net negative charge due to the dissociated carboxylate ions at pH 6.8 with strong repulsive electrostatic forces between the rhamnolipid molecules. This negative charge is shielded by the Na⁺ ions in the electrical double layer in the presence of NaCl, causing the formation of a close-packed monolayer, and a decrease in CMC, and surface tension values. The maximum compaction is observed at 0.5 M NaCl concentrations for R1 and R2 monolayers, with the R1 monolayer more compact than R2. The larger spaces left below the hydrophobic tails of R1 with respect to that of R2, due to the missing second rhamnosyl groups are thought to be responsible for the higher compaction. The rigidity of both R1 and R2 monolayers increases with the electrolyte concentration. The rigidity of the R1 monolayer is greater than that of R2 at all NaCl concentrations due to the lower hydrophilic character of R1. The variation of CMC values as a function of NaCl concentration obtained from the surface tension measurements and critical packing parameter (CPP) calculations show that spherical micelles, bilayer and rod like micelles are formed in the rhamnolipid solutions as a function of the NaCl concentration. The results of optical microscopy supported these aggregation states indicating lamellar nematic liquid crystal, cubic lamellar and hexagonal liquid crystal phases in R1 and R2 solutions depending on the NaCl concentration.     

The effect of intramolecular‐hydrogen bonds in the synthesis of novel imidates from a 13‐membered dioxadithia crown ether diester

The synthesis and structural properties of three novel imidates, 11,13‐bis‐(2‐amino‐ethylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane ( 2 ), 11,13‐bis‐(3‐aminopropylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane, ( 3 ) and 2,11‐dioxa‐5,8‐dithia‐13,16,19,22‐tetraazabicyclo[10.10.1]tricosa‐1(22),12‐diene, ( 4 ) have been described. These compounds were synthesized by treating 1,10‐dioxa‐4,7‐dithiacyclotridecane‐11,13‐diester ( 1 ) with the appropriate diamine under N₂ and their structures have been characterised by elemental analyses, ¹H‐ and ¹³C‐nmr, ir, and mass spectral studies. Elemental analyses and spectroscopic data support the proposed imidate structures. In addition, total energy and heat of formation (Figure 2) calculated for imidates 2a‐4a and 2b‐4b by the semiempirical AM1 calculations have shown that imidates 2b‐4b having intramolecular hydrogen bonds are more stable (5‐10 kcal/mol) than compounds 2a‐4a .     

DNA Hydrolysis by Homo- and Heteronuclear Cu(II)–Ni(II) Complexes of Two Diester-type Ligands

Nucleolytic activities of novel mononuclear Cu(II), homo- and heterodinuclear Cu(II)–Ni(II) complexes with two diester-type ligands were investigated on pCYTEXP by neutral agarose gel electrophoresis. The analyses of the cleavage products obtained electrophoretically indicate that the examined complexes induce very similar conformational changes on supercoiled DNA by converting supercoiled form to nicked form. At concentrations greater than 100M, the complexes possessed effective nucleolytic activities for 10min of incubation time. However, their nucleolytic activities did not increase significantly with longer periods of incubation. The pH-nucleolytic activity profiles of the complexes differed significantly. Metal complex induced DNA cleavage was also tested for inhibition by various radical scavengers. It could be proposed from the data that diffusible intermediate oxidants are not involved in these reactions or they are not necessary for DNA cleavage since none of antioxidants inhibited DNA cleaving activities of the complexes.     

Characterization of glucoamylase immobilized on celite

Immobilization of glucoamylase (EC 3.2.1.3) on Celite R649 bio-catalyst carrier for hydrolysis of maltose and maltodextrin has been investigated in both packed bed and recirculated batch reactors. The kinetics parameters on the hydrolysis of maltose were estimated from the packed bed reactor. It is found that this immobilized enzyme is as efficient as the soluble enzyme in catalyzing hydrolysis of maltose. However, it is less efficient than the soluble enzyme in hydrolyzing 30% (w/v) maltodextrin, giving a maximum dextrose equivalent (DE) value of 96.0% instead of 98.2%.     

Synthesis and determination of pKa values of some new 3,4-disubstituted-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives in non-aqueous solvents

3-Alkyl(Aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) reacted with 2-furoyl chloride and thiophene-2-carbonyl chloride to afford the corresponding 3- alkyl(aryl)-4-(2-furoylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (3) and 3-alkyl(aryl)- 4-(2-thienylcarbonylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (4), respectively. The new compounds synthesized were characterized by using IR, 1H-NMR, 13C-NMR and UV spectral data together with elemental analysis. In addition, to investigate the effects of solvents and molecular structure upon acidity, compounds 3 and 4 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents (isopropyl alcohol, tert-butyl alcohol, N,N-dimethylformamide and acetonitrile). The half-neutralization potential values and the corresponding pKa values were determined for all cases.     

Synthesis and structural studies of (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}pyridin-2-yl)imino]butan-2-one oxime, ligand and its mono-, di- and trinuclear copper(II) complexes

A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H₂Pymdo) (3) has been synthesized in H₂O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H₂Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H₂Pymdo) and its copper(II) complexes were characterized by ¹H-n.m.r., ¹³C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H₂Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H₂Pymdo and its Cu(II) complexes.