Experiences in the measurement of RBC-bound IgG as markers of cell age

An immunologically mediated pathway has been largely accepted to be one of the mechanisms involved in the clearance of senescent or prematurely damaged RBC. According to this pathway, RBC removal is mediated by binding of naturally occurring IgG to clustered integral membrane proteins, followed by complement deposition. The validation of an immunoenzymatic method for the detection of RBC-bound autologous IgG is presented. The use of RBC-bound IgG as an index related to red cell age was evaluated by measuring IgG binding in RBC treated with the clustering agent ZnCl2, in density fractionated RBC and in a selected group of patients expected to have an altered RBC life span. The immunoenzymatic method for IgG detection resulted to be reproducible (CV = 3.4%). IgG binding to in vitro clustered RBC was found to be enhanced to a very great extent, about 20 times higher with respect to untreated RBC. A slight but significant increase (about 1.8-fold) in membrane-bound IgG was observed in the highest density fraction of normal RBC, which constituted 1% of the total cells. A significantly greater number of RBC-bound IgG was measured in splenectomized beta-thalassemia intermedia patients and in subjects with secondary decreases in the C3 complement fraction concentration.     

Use of the diphasic dialysis as a new extraction procedure in the determination of enrofloxacin and ciprofloxacin in egg

We have developed a new method for the analysis of the fluoroquinolones enrofloxacin and ciprofloxacin in eggs using a diphasic dialysis procedure as extraction and purification method. High pressure liquid chromatography-mass spectrometry (HPLC-MS) was used for the confirmatory determination of these compounds. The method was found to be linear between 10 and 800 ng g⁻¹ for enrofloxacin, and between 20 and 1600 ng g⁻¹ for ciprofloxacin. The recovery percentages were in the 70-104% range for enrofloxacin, and 55-97% for ciprofloxacin. The assay described was repeatable and reproducible with a limit of quantitation of 2 and 4 ng g⁻¹ for enrofloxacin and ciprofloxacin from egg, respectively.     

Mechanisms of acid decomposition of dithiocarbamates. 3. Aryldithiocarbamates and the torsional effect

The acid decomposition of some p-substituted aryldithiocarbamates (arylDTCs) was observed in 20% aqueous ethanol at 25 degrees C, mu = 1.0 (KCl, for pH > 0). The pH-rate profiles showed a dumbell shape with a plateau where the observed first-order rate constant k(obs) was equal to k(o), the rate constant of the decomposition of the dithiocarbamic acid species. The acid dissociation constants of the dithiocarbamic acids (pK(a)) and their conjugate acids (pK(+)) were calculated from the pH-rate profiles. Comparatively, k(o) was more than 10(4)-fold faster than alkyldithiocarbamates (alkDTCs) with similar pK(N) (the acid dissociation constant of the parent amine). It was observed that the values of pK(a) and pK(+)were 5 and 8 units of pK, respectively, higher than the expected values from the pK(N) of alkylDTCs. The higher values were attributed to the inhibition of the delocalization of the nitrogen electron pair into the benzene ring because of the strong electron withdrawal effect of the thiocarbonyl group. Comparison of the activation parameters showed that the rate acceleration was due to a decrease in the enthalpy of activation. Proton inventory indicated the existence of a multiproton transition state, and it was consistent with an S to N proton transfer through a water molecule. There are two hydrogens contributing to a secondary SIE, and there are also two protons that are being transferred at the transition state to form a zwitterion followed by fast C-N bond cleavage. The mechanism could also be a concerted asynchronic process where the N-protonation is more advanced than the C-N bond breakdown. The kinetic barrier is similar to the torsional barrier of thioamides, suggesting that the driving force to reach the transition state is the needed torsion of the C-N bond that inhibits the resonance with the thiocarbonyl group and the aromatic moiety, increasing the basicity of the nitrogen and making the proton transfer thermodynamically favorable.     

Zinc(II), cadmium(II) and mercury(II) halide pyrrolidine-2-thione complexes

Summary White crystalline complexes of general formula ML₂X₂, where M = Zn, Cd, Hg; X = Cl, 13r, I and L = pyrrolidine-2-thione, were prepared and studied by i.r. spectroscopy in the 4000-200 cm^–1 range. Evidence for coordination of the ligand to the metal through sulphur was found in each case. The previous assignment of the band present in the ligand at 1110 cm^–1 to the(CS) fundamental is discussed.This work was supported by the National Research Council (C.N.R.) of Italy.     

Synthesis of conjugated polyrotaxanes

A series of conjugated polyrotaxane insulated molecular wires are synthesised by aqueous Suzuki polymerisation, using hydrophobic binding to promote threading of the cyclodextrin units. These polyrotaxanes have conjugated polymer cores based on poly(para-phenylene), polyfluorene, and poly(diphenylene-vinylene), threaded through 0.9-1.6 cyclodextrins per repeat unit. Bulky naphthalene-3,6-disulfonate endgroups prevent the macrocycles from slipping off the conjugated polymer chains. Dialysis experiments show that the cyclodextrins become unthreaded only if smaller stoppers are used. MALDI TOF mass spectra detect oligomers with up to ten threaded cyclodextrins, and reveal the presence of some defects that result for oxidative homo-coupling of boronic acids. Weight-average molecular weights were determined by analytical ultracentrifugation, demonstrating that step-growth polymerisation is efficient enough to achieve degrees of polymerisation up to approximately 20 repeat units (84 para-phenylenes). The fluorescence spectra of these polyrotaxanes indicate that the presence of the threaded cyclodextrin macrocycles reduces the flexibility of the conjugated polymer pi-systems. Both the solution and the solid-state photoluminescence quantum yields are enhanced upon threading of the conjugated polyaromatic cores through alpha- or beta-cyclodextrins, and the emission spectra of the polyrotaxanes are blue-shifted compared to the corresponding unthreaded polymers. The greater weight of the 0-0 transition in the emission spectra, as well as the smaller Stokes shift, indicate that the polyrotaxanes are more rigid than the unthreaded polymers.     

Solidification of metallic tin in dispersed phase

Differential scanning calorimetry (DSC) and particle size measurements were carried out on disproportionation products of pure SnO to investigate the fusion and solidification behaviour of Sn droplets and their catalytic nucleation on Sn oxides. If disproportionation reaction takes place at T ≥ 798 K, the products are metallic Sn and SnO₂; but for 523 < T < 798 K, SnO₂ is replaced by an intermediate oxide (IO) Sn_xO_(1+x). On melting, samples with IO show a drop of melting point of metallic tin due to Gibbs–Thomson effect; no lowering of melting point was observed in samples with SnO₂. On the other hand, if solidification occurs in the presence of IO, Tin droplets always displayed three distinct exothermic solidification peaks, but if it takes place in the presence of SnO₂, only one exothermic peak is observed. Undercooling values and contact angles were determined for each of the heterogeneous nucleation processes. The different behaviour of metallic Tin droplets was related to the different lattice symmetry of SnO₂ and IO, which act as nucleation catalysts.     

New Cisplatin Analogues—On the Way to Better Antitumor Agents

The clinical success of cisplatin (cis -diamminedichloroplatinum(II )) in antitumor chemotherapy has encouraged an all-out search for analogues with lower toxicity, improved therapeutic index and increased activity. Literally thousands of analogues, obtained by replacement of the ammine- and chloro-ligands by other amines and anionic ligands, respectively, have been systematically screened for activity in experimental tumor models. Some of these analogues have been selected for clinical evaluation, but only very few of them appear to be promising antitumor agents. More recently, cisplatin analogues have been designed and synthesized on the basis of, inter alia, the following considerations: 1) platinum complexes with carrier molecules as ligands should prove useful for achieving increasing drug concentration in tumor tissues; 2) platinum complexes with chemotherapeutic agents as ligands could afford polyfunctional drugs with synergistic action; 3) complexes containing more than one platinum atom might be more effective than complexes containing only one platinum atom; 4) platinum complexes could be used as sensitizers in radiation therapy. In this paper, we shall give a brief account of the “traditional” analogues, and then critically discuss what we believe could be the new trends in the design of cisplatin analogues.     

Novel cinchona alkaloid carbamate C9-dimers as chiral anion-exchange type selectors for high-performance liquid chromatography

Nine new quinine (QN) carbamate C9-dimers (QN-X-QN), with different aliphatic and cyclic spacers (X), have been synthesized and immobilized onto porous silica gel for HPLC. The chiral discriminating behavior of these "dimeric" anion-exchange type chiral stationary phases (CSPs) has been investigated in detail, to elucidate the role of the presence of a second QN subunit on the chiral selector (SO), as well as the influence of the structure and length of the spacer, on the overall chiral recognition of a set of N-derivatized amino acids and other acidic drugs. The bulkiness of the intermediate spacer tuned the chiral recognition abilities of these SOs, with the 1,3-adamantylen-derived CSP being the one that led to the best separations. Shorter spacers reduced the chiral discrimination abilities of the "dimeric" selectors, with the n-hexylen bridge being the most favorable distance to allow a nearly independent interaction of the two QN subunits with the racemic analytes. The comparison to five "monomeric" CSPs showed that the "dimeric" ones usually retain the chiral analytes more strongly, though the enantioseparation is not improved. Nevertheless, the exceptional resolution abilities of dimeric SOs with a trans- 1,2-diaminocyclohexylen-bridge for the separation of DNP-derivatives of amino acids and certain acidic drugs of therapeutical interest (e.g., profens) seemed to be superior to most of the other CSPs.     

Thermal decomposition of some imidazole and N-methyl substituted imidazole complexes of palladium(II)

We describe in this paper the thermal decomposition in air of several complexes of palladium(II) chloride with imidazole and N-methylimidazole. Although the final process of the decomposition gives (PdCl₂)_n which then decomposes to pa ladium which oxidizes to PdO, there are interesting differences in the initial decomposition path. The reasons for these differences appear to be related to the trans-effect and to the presence in the imidazole complexes of hydrogen bonds which break down at temperatures of around 220.

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Zusammenfassung In diesem Beitrag wird die thermische Zersetzung verschiedener Komplexe des Palladium(II)chlorids mit Imidazol und N-Methylimidazol in Luft beschrieben. Obwohl der Endvorgang der Zersetzung (PdCl₂)_n ergibt, welches dann zu Palladium zersetzt und zu PdO oxidiert wird, bestehen interessante Unterschiede im Anfangsschritt der Zersetzung. Die Ursachen dieser Unterschiede scheinen mit dem Trans-Effekt und der Anwesenheit von Wasserstoffbindungen in den Imidazolkomplexen verbunden zu sein, welche bei Temperaturen um 220 zerstört werden.

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Résumé La décomposition thermique dans l'air de plusieurs complexes du chlorure de palladium(II) avec l'imidazole et le méthyl-4-imidazole est décrite. Bien que l'étape finale de la décomposition donne (PdCl₂)_n qui se décompose ensuite en palladium qui s'oxyde en PdO, des différences intéressantes apparaissent dans les étapes initiales de la décomposition. Les causes de ces différences sont en rapport avec l'effet trans et la présence, dans les complexes avec l'imidazole, de liaisons hydrogÊne qui se rompent vers 220.

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(II) -. (PdCl₂)_n, , PdO, . , - , 220.

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One of us (M.C. Navarro Ranninger) would like to thank the D.G.E.S.I. for a grant that allowed her to work on this research.     

Selenium dioxide oxidation of tetrahydro-β-carboline derivatives

The oxidation of some tetrahydro-β-carboline derivatives with selenium dioxide led to the formation of 1,4-dihydro or fully aromatic β-carbolines, depending on the nature and the number of substituents at 1 position. The oxidation of 2-acetyl derivatives followed a different course and the products originated by the attack at C-1 of the ring C of the tetrahydro-β-carboline were obtained.