Mineral content and botanical origin of Spanish honeys

Eleven elements (Zn, P, B, Mn, Mg, Cu, Ca, Ba, Sr, Na and K) were determined by inductively plasma coupled spectrometry in 40 honey samples from different places of Spain and four different botanical origins: Eucalyptus (Eucalyptus sp.), Heather (Erica sp.), Orange-blossom (Citrus sinensis) and Rosemary (Rosmarinus officinalis). K, Ca and P show the higher levels with average concentrations ranged between 434.1-1935 mg kg⁻¹ for K; 42.59-341.0 mg kg⁻¹ for Ca and 51.17-154.3 mg kg⁻¹ for P. Levels of Cu (0.531-2.117 mg kg⁻¹), Ba (0.106-1.264 mg kg⁻¹) and Sr (0.257-1.462 mg kg⁻¹) are the lowest in all honey samples. Zn (1.332-7.825 mg kg⁻¹), Mn (0.133-9.471 mg kg⁻¹), Mg (13.26-74.38 mg kg⁻¹) and Na (11.69-218.5 mg kg⁻¹) concentrations were found strongly dependent on the kind of botanical origin.Results were submitted to pattern recognition procedures, unsupervised methods such as cluster and principal components analysis and supervised learning methods like linear discriminant analysis in order to evaluate the existence of data patterns and the possibility of differentiation of Spanish honeys from different botanical origins according to their mineral content. Cluster analysis shows four clusters corresponding to the four botanical origins of honey and PCA explained 71% of the variance with the first two PC variables. The best-grouped honeys were those from heather; eucalyptus honeys formed a more dispersed group and finally orange-blossom and rosemary honeys formed a less distinguishable group.     

Computation in kinetics, III. A new method for kinetic model search based on simultaneous regression estimation of rate constants, stoichiometry and/or reaction order

Modified samples of natural mordenites have been found to catalyze the oxidative condensation of methane to yield ethane and ethylene. The selectivity towards C₂ hydrocarbons increases, whereas the acidity of zeolites falls.

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, . C₂ .

     

Equilibrium and Kinetics of NO and CO Chemisorptions on Nonstoichiometric Nickel-Copper Manganites

The equilibrium and kinetics of adsorption of NO and CO on nonstoichiometric nickel-copper manganites have been investigated through volumetric measurements. The adsorption isotherms were satisfactorily fitted to the Freundlich equation. The equilibrium coverages at 298 K were found to depend closely on the chemical composition of the oxide; thus, a decrease in the coverage beyond a maximum copper extent was observed. The adsorption isotherms of NO at various temperatures in the range from 298 to 473 K showed that the equilibrium coverage decreases with increasing temperature. This behavior enabled us to follow the logarithmic decrease of the heat of adsorption of NO on such surfaces. The adsorptions of NO and CO on surfaces preadsorbed with CO and NO, respectively, were also studied. These experiments showed the ability of NO to displace CO preadsorbed molecules whereas the contrary did not hold, suggesting the existence of common adsorption sites as well as some specific CO adsorption sites. Finally, some kinetic data are reported showing that the experimental adsorption results fit the Elovich equation (with t(0) approximately 0), although two distinct rate processes could be identified. Copyright 2000 Academic Press.     

Synthesis and supramolecular properties of molecular clips with anthracene sidewalls

Novel molecular clips with anthracene sidewalls (1 a-c) were synthesized; they form stable host-guest complexes with a variety of electron-deficient aromatic and quinoid molecules. According to single-crystal structure analyses of clip 1 c and 1,2,4,5-tetracyanobenzene (TCNB) complex 14@1 b, the clips' anthracene sidewalls have to be compressed substantially during the complex formation to provide attractive pi-pi interactions between the aromatic guest molecule and the two anthracene sidewalls in the complex. The compression and expansion of aromatic sidewalls are calculated by molecular mechanics to be low-energy processes, so the energy required for compression of the anthracene sidewalls during complex formation is apparently overcompensated by the gain in energy resulting from the attractive pi-pi interactions. The finding that complexes of the clips 1 a-c are more stable than those of the corresponding clips 2 a-c can be explained in terms of the larger van der Waals contact surfaces of the anthracene sidewalls in 1 a-c (relative to the naphthalene sidewalls in 2 a-c). Color changes resulting from charge-transfer (CT) bands are observed in complex formation by 1 a-c: from colorless to red or purple with TCNB (14), and from yellow to green with 2,4,7-trinitro-9-fluorenone TNF (17). Independently, the host 1 b and guest 14 fluoresce from their respective excited singlet states, whilst in the complex 14@1 b the charge-transfer state quenches the higher-energy singlet states of the two components, and as a result luminescence is only observed from this new CT state. To the best of our knowledge, complex 14@1 b is the first example of CT luminescence from a host-guest complex. The binding constant determined for the formation of the TCNB complex 14@1 b from a UV/Vis titration experiment (Ka = 12 400 m(-1)) agrees well with the value (K(a) = 12 800 m(-1)) obtained by 1H NMR titration.     

Measuring the electrophoretic mobility of concentrated suspensions in nonaqueous media

We present a new method of measuring the electrophoretic mobility of a particle in a concentrated suspension. The method is used to measure the electrophoretic mobility of PMMA particles (diameter 10 microm) suspended in a mixture of liquid hydrocarbons. The particle volume fraction of the suspension is varied from 0 up to 0.30 and the resulting variation of the electrophoretic mobility is discussed. The suspending liquid is such that its refractive index is very close to that of the particles. Thus the suspension is almost transparent and it is possible to follow through a microscope the motion of one particle. The suspension is subjected to a low-frequency electric field (0.5 Hz). The cell containing the suspension is mounted on a piezoelectric crystal. The displacement that compensates for the particle motion (when the particle image is steady) is determined.     

Design, synthesis, and photophysical studies of a porphyrin-fullerene dyad with parachute topology; charge recombination in the marcus inverted region

As part of a continuing investigation of the topological control of intramolecular electron transfer (ET) in donor-acceptor systems, a symmetrical parachute-shaped octaethylporphyrin-fullerene dyad has been synthesized. A symmetrical strap, attached to ortho positions of phenyl groups at opposing meso positions of the porphyrin, was linked to [60]-fullerene in the final step of the synthesis. The dyad structures were confirmed by (1)H, (13)C, and (3)He NMR, and MALDI-TOF mass spectra. The free-base and Zn-containing dyads were subjected to extensive spectroscopic, electrochemical and photophysical studies. UV-vis spectra of the dyads are superimposable on the sum of the spectra of appropriate model systems, indicating that there is no significant ground-state electronic interaction between the component chromophores. Molecular modeling studies reveal that the lowest energy conformation of the dyad is not the C(2)(v)() symmetrical structure, but rather one in which the porphyrin moves over to the side of the fullerene sphere, bringing the two pi-systems into close proximity, which enhances van der Waals attractive forces. To account for the NMR data, it is proposed that the dyad is conformationally mobile at room temperature, with the porphyrin swinging back and forth from one side of the fullerene to the other. The extensive fluorescence quenching in both the free base and Zn dyads is associated with an extremely rapid photoinduced electron-transfer process, k(ET) approximately 10(11) s(-)(1), generating porphyrin radical cations and C(60) radical anions, detected by transient absorption spectroscopy. Back electron transfer (BET) is slower than charge separation by up to 2 orders of magnitude in these systems. The BET rate is slower in nonpolar than in polar solvents, indicating that BET occurs in the Marcus inverted region, where the rate decreases as the thermodynamic driving force for BET increases. Transient absorption and singlet molecular oxygen sensitization data show that fullerene triplets are formed only with the free base dyad in toluene, where triplet formation from the charge-separated state is competitive with decay to the ground state. The photophysical properties of the P-C(60) dyads with parachute topology are very similar to those of structurally related rigid pi-stacked P-C(60) dyads, with the exception that there is no detectable charge-transfer absorption in the parachute systems, attributed to their conformational flexibility. It is concluded that charge separation in these hybrid systems occurs through space in unsymmetrical conformations, where the center-to-center distance between the component pi-systems is minimized. Analysis of the BET data using Marcus theory gives reorganization energies for these systems between 0.6 and 0.8 eV and electronic coupling matrix elements between 4.8 and 5.6 cm(-)(1).     

Investigations of a novel process to the framework of benzo[c]cinnoline

A novel synthetic process leading to the framework of benzo[c]cinnoline has been discovered and investigated. The process is composed of two separate reactions, the first of which is a partial reduction of the nitro groups of the 2,2'-dinitrobiphenyl, a process that we believe proceeds via a SET mechanism to yield the hydroxyamino and nitroso groups. In the following step the cyclization takes place under formation of the -N=N- bond. We believe that this process take place via a radical mechanism through the nitroso radical anion. The novel process affords either benzo[c]cinnoline or benzo[c]cinnoline N-oxide, both in high yields, 93% and 91%, respectively. To obtain benzo[c]cinnoline, the reaction is conducted with an alcohol as solvent and an alkoxide as the base, while for benzo[c]cinnoline N-oxide, water is used as solvent with sodium hydroxide as the base. To establish the latter procedure, statistical experimental design and multivariate modeling were utilized to reveal the response surface for the reaction and to determine the optimal conditions for the reaction. A proposal for the complex reaction mechanism is given. During the corroboration of the mechanism, a new deoxygenation reaction for converting benzo[c]cinnoline N-oxide into benzo[c]cinnoline was discovered. The reaction is conducted by treating the N-oxide with sodium ethoxide at elevated temperature to achieve near-quantitative conversion into benzo[c]cinnoline in a yield of 96%.     

Affinity capillary electrophoresis study of the linkage existing between proton and zinc ion binding to bacitracin A1

Measurements by capillary electrophoresis (CE) of bacitracin A(1) effective mobility at different pH values permitted to estimate the five acidic dissociation constants and the Stokes radii at different protonation stages of the macrocyclic dodecapeptide. The pK(a) values were 3.6 and 4.4 for the two carboxylic groups of the lateral chains of D-Asp-11 and D-Glu-4, respectively, 6.4 for the aza-atom of the imidazole ring of His-10, 7.6 for the amino group of N-terminal Ile-1 and 9.7 for the delta-amino group of D-Orn-7, very close to the values obtained by other researchers by titration experiments. In agreement with a rigid macrocyclic structure the Stokes radii of different protonated forms ranged only between 14.3 and 14.8 A. Best fitting procedures performed on experimental mobility measured at two different pH values (5.50 and 6.72) in the presence of increasing Zn(+2) concentration allowed confirming the model that assumes the binding of Zn(+2) to P(0) peptide form with a 1.5 x 10(3) M(-1) intrinsic association constant. Following to Zn(+2) binding, the pK(a) of the amino group of N-terminal Ile-1 is shifted from 7.6 to 5.9 and the Stokes radius is reduced of about 3 A. The mean charge of the bacitracin A(1)-Zn(+2) complex resulted +1.67 and +1.12 at pH 5.50 and 6.72, respectively. These results suggest that the amino group of N-terminal Ile-1 is not essential for Zn(+2) binding.     

Axial Imidazole Distortion Effects on the Catalytic and Binding Properties of Chelated Deuterohemin Complexes

The effect of strain in the axial coordination of imidazole to the heme has been studied in the chelate complexes deuterohemin-histidine (DH-His) and deuterohemin-alanylhistidine (DH-AlaHis). Molecular mechanics calculations indicate that three types of distortion of the axial ligand occur in DH-His, due to the relatively short length of the arm carrying the donor group: tilting off-axis, tipping, and inclination of the imidazole plane with respect to the axial Fe-N bond. The effects of tilting (Deltagamma approximately 10 degrees ) and inclination of the imidazole ring (Deltadelta approximately 17 degrees ) are dominant, while tipping is small and is probably of little importance here. By contrast, the axial imidazole coordination is normal in DH-AlaHis and other computed deuterohemin-dipeptide or -tripeptide complexes where histidine is the terminal residue, the only exception being DH-ProHis, where the rigidity of the proline ring reduces the flexibility of the chelating arm. The distortion in the axial iron-imidazole bond in DH-His has profound and negative influence on the binding and catalytic properties of this complex compared to DH-AlaHis. The former complex binds more weakly carbon monoxide, in its reduced form, and imidazole, in its oxidized form, than the latter. The catalytic efficiency in peroxidative oxidations is also reduced in DH-His with respect to DH-AlaHis. The activity of the latter complex is similar to that of microperoxidase-11, the peptide fragment incorporating the heme that results from hydrolytic cleavage of cytochrome c.     

Monocarbonyl cationic rhodium(I) complexes

Summary The preparations and characterisation of cationic complexes of the type [Rh(CO)(MeCN)(PR₃)₂]ClO₄, [Rh(CO)L(PR₃)₂]ClO₄ (L=py or 2-MeOpy), [Rh(CO)(L-L)(PR₃)₂]ClO₄ (L-L = bipy or phen) and [Rh(CO)(PR₃)₃]ClO₄ with PR₃ = P(p-YC₆H₄)₃ (Y=Cl, F, Me or MeO) are described.