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.     

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.     

Synthesis,conformational analysis and in vivo assays of an anti-cancer vaccine that features an unnatural antigen based on an sp2-iminosugar fragment

The Tn antigen (GalNAc-α-1-O-Thr/Ser) is a well-known tumor-associated carbohydrate determinant. The use of glycopeptides that incorporate this structure has become a significant and promising niche of research owing to their potential use as anticancer vaccines. Herein, the conformational preferences of a glycopeptide with an unnatural Tn antigen, characterized by a threonine decorated with an sp²-iminosugar-type α-GalNAc mimic, have been studied both in solution, by combining NMR spectroscopy and molecular dynamics simulations, and in the solid state bound to an anti-mucin-1 (MUC1) antibody, by X-ray crystallography. The Tn surrogate can mimic the main conformer sampled by the natural antigen in solution and exhibits high affinity towards anti-MUC1 antibodies. Encouraged by these data, a cancer vaccine candidate based on this unnatural glycopeptide and conjugated to the carrier protein Keyhole Limpet Hemocyanin (KLH) has been prepared and tested in mice. Significantly, the experiments in vivo have proved that this vaccine elicits higher levels of specific anti-MUC1 IgG antibodies than the analog that bears the natural Tn antigen and that the elicited antibodies recognize human breast cancer cells with high selectivity. Altogether, we compile evidence to confirm that the presentation of the antigen, both in solution and in the bound state, plays a critical role in the efficacy of the designed cancer vaccines. Moreover, the outcomes derived from this vaccine prove that there is room for exploring further adjustments at the carbohydrate level that could contribute to designing more efficient cancer vaccines.

An anti-cancer vaccine based on an unnatural antigen with an sp²-iminosugar fragment.     

Direct mass spectrometry of polymers. XIV. Thermal fragmentation processes in poly-schiff bases

The thermal fragmentation processes in poly-Schiff bases have been investigated by direct pyrolysis–mass spectrometry. The mass spectral data show that the thermal fragmentation occurring in the polymers under investigation is characterized by hydrogen transfer reactions. In the case of a totally aromatic poly-Schiff base (polymer I ), the thermal fragmentation process involves hydrogen transfer irom the methyne group with formation of fragments bearing nitrile and/or phenyl end groups. In the case of aromatic-aliphatic poly-Schiff bases (polymers II–IV ), the hydrogen transfer process occurs from the aliphatic methylene groups. The latter process involves a lower energy and therefore occurs at lower temperatures with respect to the totally aromatic polymer I , with formation of thermal fragments bearing olefin and/or imine end groups. Beside these fragments, several thermal fragmentation compounds are also evolved by multiple hydrogen transfer reactions.     

On the growth and shape of sodium taurodeoxycholate micellar aggregates: a spin-label and quasielastic light scattering investigation

Electron spin resonance (ESR) and quasielastic laser scattering (QELS) measurements have been carried out on sodium taurodeoxycholate (NaTDC) micellar aqueous solutions. Computer simulation of the ESR line shape has been used to quantitatively analyze the rotational dynamics of the cholestan-spin label (CSL) dissolved by the NaTDC micellar aggregates as a function of temperature and NaCl concentration. The local reorientation of CSL has been accounted for motionally-averaged g- and A-tensors assuming fast oscillation around the spin-probe long molecular axis. The overall Brownian tumbling of CSL-micelle complexes has been modeled by an axially symmetric rotational tensor. Good agreement with experimental spectra is obtained. Best-fit rotational parameters and QELS data suggest that, in the circumstance of large aggregation, NaTDC micelles have cylindrical shape and micellar growth occurs along the cylinder axis.     

Synthesis and Characterization of Pyrrolthiosemicarbazone Complexes of Palladium(II). Crystal Structures of [{Pd[C4H4NC(H)=NNC(S)NHMe](Cl)}2{μ‐Ph2P(CH2)3PPh2}] and [Pd{C4H4NC(H)=NNC(S)NHMe}{Ph2P(CH2)2PPh2‐P,P}](Cl)

Reaction of the thiosemicarbazone ligands C₄H₄NC(H)=NN(H)C(S)NHR (R = Me, a ; Et, b ) with Li₂[PdCl₄] gave the dinuclear complexes [Pd{C₄H₄NC(H)=NNC(S)NHR}(μ‐Cl)]₂ (R = Me, 1a ; Et, 1b ) with a central Pd₂Cl₂ core and with deprotonation of the thiosemicarbazones at the hydrazinic nitrogen atom. Treatment of 1a and 1b with triphenylphosphine gave the mononuclear compounds [Pd{C₄H₄C(H)=NNC(S)NHR}(Cl)(PPh₃)] (R = Me, 2a ; Et, 2b ), whereas reaction of 1a and 1b with tertiary diphosphines gave mono‐ and dinuclear compounds, as appropriate, with the corresponding diphosphine acting as a monodentate ( 6b ), chelating ( 3a ) and bridging ligand ( 4a, 5a , 4b, 5b ). Treatment of 1a and 1b with (Ph₂PCH₂CH₂PPh₂)W(CO)₅ gave the new heterobimetallic complexes 7a and 7b . The crystal structures of complexes 3a and 4a are described.     

Tricarbonyl Complexes of Rhenium(I) with Acetylpyridine Benzoylhydrazone and Related Ligands

Novel rhenium(I) tricarbonyl complexes have been prepared by reactions of (Et₄N)₂[Re(CO)₃Br₃] with acetylpyridine benzoylhydrazone, Hapbhyd, di(2‐pyridyl)ketone benzoylhydrazone, Hpy₂bhyd, bis(2‐pyridine)ketone, py₂CO, and pyridinealdehyde terephtalaldehydebishydrazone, pytehyd. The ligands remain protonated when no supporting base is added and the following complexes have been isolated: [Re(CO)₃Br(Hapbhyd)], [Re(CO)₃Br(Hpy₂bhyd‐py, hyd)], [Re(CO)₃Br(Hpy₂bhyd‐py¹, py²)], [Re(CO)₃Br(py₂CO‐N, N)] and [Re(CO)₃Br(pytehyd)]. Addition of triethyl amine results in deprotonation of Hapbhyd and the formation of [Re(CO)₃(OH₂)(apbhyd)], whereas Hpy₂bhyd is hydrolysed and a rhenium complex with the monoanionic bis(2‐pyridyl)hydroxymethanolato ligand, {py₂C(OH)O}^‐, is formed. The same compound, [Re(CO)₃{py₂C(OH)O}], is obtained when triethyl amine and water are added to a mixture of (Et₄N)₂[Re(CO)₃Br₃] and py₂CO. The air‐stable products have been studied by spectroscopic methods and X‐ray crystallography.     

Combining fixed- and moving-grid methods to study direct dissociation processes involving nonadiabatic transitions

We present a novel quantum-dynamics approach suitable for computing direct dissociation processes, including electronic transitions. This approach combines quantum trajectories in the Lagrangian reference frame with standard fixed-grid wave packets in order to overcome the limitations and difficulties of both techniques. As a model application, we consider the ultrafast photodissociation of H2 excited by a femtosecond extreme UV laser pulse.     

Copper-assisted oxidation of catechols into quinone derivatives

Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.

An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper.