Binding of amino acids into a novel multiresponsive ferrocene receptor having an ene backbone

[reaction: see text] Receptor 1 featuring two open arms, multipoint binding sites, and unsaturated linkers on a ferrocene platform shows strong 1:1 binding to unprotected alpha-amino acids (UV-vis, fluorescence, CV, ITC, NMR, and ESI-MS). NMR and ESI-MS studies suggest an encapsulative binding mode involving the alpha,beta-unsaturated carbonyl residue (site for -NH3+, interaction A) and the terminal -OH groups (site for -COO-, interaction B).     

Determination of aflatoxins in food by overpressured-layer chromatography

Legislative measures for monitoring and control of aflatoxin levels in foods and foodstuffs have been introduced in many countries. The aim of the present work was to make developments in the field of aflatoxin analysis, focusing upon the use of overpressured-layer chromatography (OPLC) for quantitative determination. OPLC methods have been developed for the determination of aflatoxins B1, B2, G1, G2 in different foods. These methods are suitable for sample clean-up and separation as well. Using OPLC we could analyze 10 samples simultaneously. The methods were investigated with fish, corn and wheat samples spiked with 2-10 ng/g aflatoxins. Quantitative evaluation of aflatoxins was accomplished by densitometry. Average recoveries from each food were greater than 73%. The OPLC technique seems to be a rapid, reproducible and cost-effective analysis for quantitative determination of aflatoxins in foods.     

Synthesis of multifunctional copolymers of poly(methylphenylsilane) with (R)-N-(1-phenylethyl)methacrylamide,disperse red 1 methacrylate and their optical and photoluminescence properties

Abstract

We report the synthesis and characterization of multifunctional polysilane copolymers containing chiral and azobenzene chromophore as a pendant group. Multifunctional polymers of poly(methylphenylsilane) (PMPS) with (R)-N-(1-phenylethyl)methacrylamide (R-NPEMAM) and disperse red 1 methacrylate (DR1MA) were synthesized in a quartz tube using UV-technique. The molecular weights of such synthesized copolymers were found to be in the order of 10³. The appearance of two glass transition temperatures in DSC indicated that the synthesized copolymers are block copolymers. The electronic absorbance of synthesized polymers was observed at 272?nm (π-π* transition of aromatic ring), 330?nm (σ-σ* transition of Si-Si chain of PMPS) and 475?nm (n-π* with π-π* transition due to azobenzene chromophore of DR1MA unit). The chirality of the synthesized polymer was confirmed through circular dichroism observed at 261?nm. Induced chirality appeared at 330?nm and 470?nm due to the association of the Si-Si chain of PMPS and the presence of azobenzene chromophore of the DR1MA unit respectively. The photoluminescence (PL) properties of the synthesized copolymers (SCDRDM-1B, SCDRDM-2B, and SCDRDM-3B) were observed at 307?nm and 415?nm when excited at 275?nm. The λem was also observed at 415?nm when excited by 325?nm. The multi-emission spectra appeared at 500?nm, 550 and 590?nm are presumed to be due to exciton coupling between azobenzene chromophore of DR1MA, and Si-Si σ-conjugation in association with the aromatic ring of PMPS and chiral unit R-NPEMAM block.     

A quasi-tetrahedral Cu4 cluster and a helical-chain copper (II) complex with single syn-anti carboxylate bridges: crystal structure and magnetic properties

A tridentate Schiff base carboxylate ligand, derived from the condensation of pyridine 2-carboxaldehyde with anthranilic acid, reacts with copper trifluoroacetate salt to give rise to the helical chain complex [Cu(C(13)H(9)N(2)O(2))(F(3)CCO(2))](n)() (1) and with copper nitrate to give rise to the tetranuclear complex [[Cu(4)(C(13)H(9)N(2)O(2))(4)(H(2)O)(4)].3.5NO(3).0.5N(3)] (2) with the addition of azide salt. The structures of these complexes have been solved by X-ray crystallography. The Cu(II) ions are in a distorted square-pyramidal environment in complex 1. They are sequentially bridged by carboxylate groups in the syn-anti conformation, resulting in the formation of an infinite helix like chain along the crystallographic c-axis. The crystal structure of complex 2 consists of tetranuclear [Cu(4)(L)(4)(H(2)O)(4)](4+) (L = C(13)H(9)N(2)O(2)(-)) cations and isolated NO(3)(-) and N(3)(-) anions in the ratio 1:3.5:0.5, respectively, involving bridging carboxylate groups in the syn-anti conformation. For 1 the carboxylato-Cu(II) coordination is apical-basal, while for 2 it is basal-basal. From the magnetic susceptibility measurements the complex 1 is found to exhibit very weak antiferromagnetic interaction whereas a weak ferromagnetic coupling has been established for complex 2. The magnetic behavior can be satisfactorily explained on the basis of the structural data for these and related complexes.     

Kinetics and mechanism of nucleophilic substitution of dichloro{1-methyl-2-(arylazo)imidazole}palladium(II) by pyridine bases

The reaction of dichloro{1-methyl-2-(arylazo)imidazole}palladium(II), Pd(RaaiMe)Cl₂ where RaaiMe = p-R–C₆H₄N=N–C₃H₂N₂-1-Me; R = H(1), Me(2), Cl(3), with pyridine bases [RPY: R = H (a), 4-Me (b), 4-Cl (c), 2-Me (d), 2,6-Me₂ (e), 2,4,6-Me₃ (f)] has been studied spectrophotometrically in MeCN at 451 nm. The products (4) have been isolated and characterised as trans-Pd(RPy)₂Cl₂. The kinetics of the nucleophilic substitution has been examined under pseudo-first-order conditions at 298 K. A single phase reaction step has been observed for bases such as Hpy (a), 4-MePy (b) and 4-ClPy (c) and follows the rate law: rate = (a + k[RPy]²[Pd(RaaiMe)Cl₂]). The bases 2-MePy (d), 2,6-Me₂Py (e) and 2,4,6-Me₃Py (f) exhibits a bi-phasic reaction and follows the rate laws: rate–1 = (a + k[RPy][Pd(RaaiMe)Cl₂]) and rate–2 = (a + k[RPy][Pd(RaaiMe)-Cl₂]), where k is the third-order rate constant; k is the second-order first phase rate constant, k is the second-order second phase rate constant and a/a/a correspond to the solvent dependent constant of the respective reaction path. The rate data supports a nucleophilic association path. External addition of Cl^– (LiCl) suppresses the rate, which follows the order: k/k/k (3) > k/k,k (1) > k/k,k (2). The k values are linearly related to the Hammett constants. The 2-substituted pyridines (d–f) remarkably reduce the rate and show a bi-phasic reaction behaviour as compared with 4-Rpy (a–c). This is attributed to the steric effect that destabilises the transition state. The rate decreases with increasing steric crowding at the ortho-position and follows the order: (d) > (f) > (e). The 4-substituted pyridines control the rate via an inductive effect and follow the order: (b) > (a) > (c).     

Solvent extraction and photometric determination of molybdenum (VI) with 2-aminobenzenethiol

A new extractive photometric method is described for estimation of molybdenum with 2-aminobenzenethiol. The green complex in chloroform has its absorbance maximum at 700 nm and is stable for 2 hr when extracted from a solution of optimum pH range 1.4-2.8. The extraction is quantitative. The sensitivity is 0.0075 microg cm (2). Beer's law is obeyed over the range 0.25-10 ppm with optimum range 0.5-4.5 ppm. The molar absorptivity is 7.08 x 10(4) 1.mole(-1). cm(-1). The overall stability constant is 2.0 x 10(8) at 25 +/- 0.1 degrees.     

Heavy and heavy to light quark expansions

We analyze the phenomenon of heavy quark condensation within the framework of the QCD sum rule approach. We discuss two alternative expansions for massive quark condensates. The first one (heavy to light quark expansion), introduced by Broadhurst and Generalis, establishes a connection between the heavy and light quark worlds. The other one (heavy quark expansion) is valid when only heavy quark systems are considered. As a byproduct we have obtained the coefficients of \(\left\langle {\bar qq} \right\rangle \) , \(\left\langle {\bar qGq} \right\rangle \) , 〈G ²〉 and 〈G ³〉 for all bilinear currents.     

Hydroxamic acid dinuclear complexes of molybdenum(V) and molybdenum(III)

Summary Molybdenum(V) and molybdenum(III) complexes [Mo₂O₃L₄] and [Mo₂L₆] derived from hydroxamic acids (HL) were prepared and identified by Raman, i.r., e.s.r., electronic spectra and analytical data. The low magnetic moments of the dinuclear complexes are due to in part to intramolecular interactions. Electronic spectra and vibrational studies indicate the presence of a Mo₂O₃ core in the molybdenum(V) complexes. The relative intensities of the, main and satellite peaks in e.s.r. spectra indicate the dinulcear nature of molybdenum(III) hydroxamates.     

Inner filter effect and the onset of concentration dependent red shift of synchronous fluorescence spectra

The phenomenon of concentration dependent red shift, often observed in synchronous fluorescence spectra (SFS) of monofluorophoric as well as multifluorophoric systems at high chromophore concentrations, is known to have good analytical advantages. This was previously understood in terms of large inner filter effect (IFE) through the introduction of a derived absorption spectral profile that closely corresponds to the SFS profile. Using representative monofluorophoric and multifluorophoric systems, it is now explained how the SF spectral maximum changes with concentration of the fluorophore. For dilute solutions of monofluorophores the maximum is unchanged as expected. It is shown here that the onset of red shift of SFS maximum of both the mono as well as the multifluorophoric systems must occur at the derived absorption spectral parameter value of 0.32 that corresponds to the absorbance value of 0.87. This value is unique irrespective of the nature of the fluorophore under study. For monofluorophoric systems, the wavelength of derived absorption spectral maximum and the wavelength of synchronous fluorescence spectral maximum closely correspond with each other in the entire concentration range. In contrast, for multifluorophoric systems like diesel and aqueous humic acid, large deviations were noted that could be explained as to be due to the presence of non-fluorescing chromophores in the system. This work bridges the entire fluorophore concentration range over which the red shift of SFS maximum sets in; and in the process it establishes the importance of the derived absorption spectral parameter in understanding the phenomenon of concentration dependent red shift of SFS maximum.