Polyamines from polyols - Pathways to azamacrocycles with hydroxymethyl pendent groups

Several pathways to macromonocylic polyamine ligands with pendent hydroxymethyl substituents have been explored. The new ligands have all been characterised by single-crystal, X-ray structure determinations on their complexes with Co(III) (one case) and Cu(II). As in some related systems, four-membered ring species, here oxetanes rather than azetidines, appear to be involved as reaction intermediates and can be quite readily isolated, providing reactants of potential for the construction of even more complicated multidentate ligands. (C) 2005 Elsevier Ltd. All rights reserved.

Synthetic, spectroscopic and X-ray crystallographic structural study of the monomeric [Cu(pysme)(sac)(MeOH)] and dimeric [Cu(6mptsc)(sac)](2) complexes [pysme = anion of the pyridine-2-carboxaldehyde Schiff base of S-methyldithiocarbazate, 6mptsc=the anio

New mixed-ligand copper(II) complexes of empirical formulas [Cu(pysme)(sac) (CH3OH)] and [Cu(6mptsc)(sac)](2) have been synthesized and characterized by conductance, magnetic, IR and electronic spectroscopic techniques. X-ray crystallographic structure analyses of these complexes indicate that in both complexes the copper(II) ions adopt a five-coordinate distorted square-pyramidal geometry with an N3SO donor environment. The Schiff bases are coordinated to the copper(II) ions as tridentate NNS chelates via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom. In the monomeric [Cu(pysme)(sac)(MeOH)] complex, the saccharinate anion acts as a monodentate ligand coordinating the copper(II) ion via the imino nitrogen atom whereas in the dimeric [Cu(6mptsc)(sac)](2) complex, the sac anion behaves as a bridging bidentate ligand providing the imino nitrogen donor atom to one of the copper(II) ions and the carbonyl oxygen as a weakly coordinated axial ligand atom to the other Cu(II) ion. In both complexes, the copper(II) ions have distorted square-pyramidal environments. The distortion from an ideal square-pyramidal geometry is attributed to the restricted bite angles of the planar tridentate ligand. (C) 2004 Elsevier Ltd. All rights reserved.

Studies of the interaction of Potassium(I), Calcium(II), Magnesium(II), and Copper(II) with Cyclosporin A

Metal ion binding properties of the immunosuppressant drug cyclosporin A have been investigated. Complexation studies in acetonitrile solution using H-1 NMR and CD spectroscopy yielded 1:1 metal-peptide binding constants (log(10)K) for potassium(l), < 1, magnesium(II), 4.8 +/- 0.2. and calcium(II), 5.0 +/- 1.0. The interaction of copper(II) with cyclosporin A in methanol was investigated with UV/visible and electron paramagnetic resonance (EPR) spectroscopy. No complexation of copper(II) was observed in neutral solution. In the presence of base, monomeric copper(II) complexes were detected. These results support the possibility that cyclosporin A has ionophoric properties for biologically important essential metal ions. (C) 2003 Elsevier Inc. All rights reserved.

Morphological features of interfacial intermetallics and interfacial reaction rate in Al-11Si-2.5Cu-(0.15/0.60)Fe cast alloy/die steel couples

Soldering reactions are commonly observed during high pressure die casting of aluminium alloys, and involve the formation and growth of interfacial intermetallics between the die and the cast alloy. It is generally believed that close to 1% Fe is necessary in the aluminium alloy to reduce soldering. However, the role of iron in the interfacial reaction has not been studied in detail. In this investigation, reaction couples were formed between H13 tool steel substrates and an Al-11Si-2.5Cu melt containing either 0.15 or 0.60% Fe. Examination revealed distinctly different intermetallic layer morphology. The overall growth and chemistry of the reaction layer and the reaction rate measured by the consumption of the substrate were compared for the two alloy melts. It was demonstrated that a higher iron content reduces the rate of interfacial reaction, consistent with an observed thicker compact ( solid) intermetallic layer. Hence, the difference in reaction rate can be explained by a significant reduction in the diffusion flux due to a thicker compact layer. Finally, the mechanism of the growth of a thicker compact layer in the higher iron melt is proposed, based on the phase relations and diffusion both within and near the interfacial reaction zone. (C) 2004 Kluwer Academic Publishers.

Synthetic, EPR spectroscopic, magnetic and X-ray crystallographic structural studies on copper(II) complexes of the tridentate N2S donor ligand formed from 6-methyl-2-formylpyridine and S-methyldithiocarbazate (Hmpsme)

New copper(II) complexes of general empirical formula, Cu(mpsme)X center dot xCH(3)COCH(3) (mpsme = anionic form of the 6-methyl-2-formylpyridine Schiff base of S-methyldithiocarbazate; X = Cl, N-3, NCS, NO3; x = 0, 0.5) have been synthesized and characterized by IR, electronic, EPR and susceptibility measurements. Room temperature mu(eff) values for the complexes are in the range 1.75-2.1 mu(beta) typical of uncoupled or weakly coupled Cu(II) centres. The EPR spectra of the [Cu(mpsme)X] (X = Cl, N-3, NO3, NCS) complexes reveal a tetragonally distorted coordination sphere around the mononuclear Cu(II) centre. We have exploited second derivative EPR spectra in conjunction with Fourier filtering (sine bell and Hamming functions) to extract all of the nitrogen hyperfine coupling matrices. While the X-ray crystallography of [Cu(mpsme)NCS] reveals a linear polymer in which the thiocyanate anion bridges the two copper(II) ions, the EPR spectra in solution are typical of a magnetically isolated monomeric Cu(II) centres indicating dissociation of the polymeric chain in solution. The structures of the free ligand, Hmpsme and the {[Cu(mpsme)NO3] center dot 0.5CH(3)COCH(3)}(2) and [Cu(mpsme)NCS](n) complexes have been determined by X-ray diffraction. The {[Cu(mpsme)NO3]0.5CH(3)COCH(3)}(2) complex is a centrosymmetric dimer in which each copper atom adopts a five-coordinate distorted square-pyramidal geometry with an N2OS2 coordination environment, the Schiff base coordinating as a uninegatively charged tridentate ligand chelating through the pyridine and azomethine nitrogen atoms and the thiolate, an oxygen atom of a unidentate nitrato ligand and a bridging sulfur atom from the second ligand completing the coordination sphere. The [Cu(mpsme)(NCS)](n) complex has a novel staircase-like one dimensional polymeric structure in which the NCS- ligands bridge two adjacent copper(II) ions asymmetrically in an end-to-end fashion providing its nitrogen atom to one copper and the sulfur atom to the other. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis and characterization of Pd(II) and Pt(II) complexes with triazolopyrimidine derivatives: The crystal structure of [Pd2L2Cl4] where L=5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

The Pd(II) and Pt(II) complexes with triazolopyrimidine C-nucleosides L-1 (5,7-dimethyl-3-(2',3',5'-tri-O-benzoyl-beta-D-ribofuranosyl-s-triazolo)[4,3-a]pyrimidine), L-2 (5,7-dimethyl-3-beta-D-ribofuranosyl-s-triazolo [4,3-a]pyrimidine) and L-3 (5,7-dimethyl[1,5-a]-s-triazolopyrimidine), [Pd(en)(L-1)](NO3)(2), (Pd(bpy)(L-1)](NO3)(2), cis-Pd(L-3)(2)Cl-2, [Pd-2(L-3)(2)Cl-4]center dot H2O, cis-Pd(L-2)(2)Cl-2 and [Pt-3(L-1)(2)Cl-6] were synthesized and characterized by elemental analysis and NMR spectroscopy. The structure of the [Pd-2(L-3)(2)Cl-4]center dot H2O complex was established by Xray crystallography. The two L-3 ligands are found in a head to tail orientation, with a (PdPd)-Pd-... distance of 3.1254(17) angstrom.L-1 coordinates to Pd(II) through N8 and N1 forming polymeric structures. L-2 coordinates to Pd(II) through N8 in acidic solutions (0.1 M HCl) forming complexes of cis-geometry. The Pd(II) coordination to L-2 does not affect the sugar conformation probably due to the high stability of the C-C glycoside bond. (c) 2006 Elsevier B.V. All rights reserved.

Does chemotherapy improve survival in high-risk Stage I and II Merkel cell carcinoma of the skin?

Purpose: The effectiveness of synchronous carboplatin, etoposide, and radiation therapy in improving survival was evaluated by comparison of a matched set of historic control subjects with patients treated in a prospective Phase II study that used synchronous chemotherapy and radiation and adjuvant chemotherapy. Patients and Methods: Patients were included in the analysis if they had disease localized to the primary site and nodes, and they were required to have at least one of the following high-risk features: recurrence after initial therapy, involved nodes, primary size greater than 1 cm, or gross residual disease after surgery. All patients who received chemotherapy were treated in a standardized fashion as part of a Phase II study (Trans-Tasman Radiation Oncology Group TROG 96:07) from 1997 to 2001. Radiation was delivered to the primary site and nodes to a dose of 50 Gy in 25 fractions over 5 weeks, and synchronous carboplatin (AUC 4.5) and etoposide, 80 mg/m(2) i.v. on Days 1 to 3, were given in Weeks 1, 4, 7, and 10. The historic group represents a single institution's experience from 1988 to 1996 and was treated with surgery and radiation alone, and patients were included if they fulfilled the eligibility criteria of TROG 96:07. Patients with occult cutaneous disease were not included for the purpose of this analysis. Because of imbalances in the prognostic variables between the two treatment groups, comparisons were made by application of Cox's proportional hazard modeling. Overall survival, disease-specific survival, locoregional control, and distant control were used as endpoints for the study. Results: Of the 102 patients who had high-risk Stage I and II disease, 40 were treated with chemotherapy (TROG 96:07) and 62 were treated without chemotherapy (historic control subjects). When Cox's proportional hazards modeling was applied, the only significant factors for overall survival were recurrent disease, age, and the presence of residual disease. For disease-specific survival, recurrent disease was the only significant factor. Primary site on the lower limb had an adverse effect on locoregional control. For distant control, the only significant factor was residual disease. Conclusions: The multivariate analysis suggests chemotherapy has no effect on survival, but because of the wide confidence limits, a chemotherapy effect cannot be excluded. A study of this size is inadequately powered to detect small improvements in survival, and a larger randomized study remains the only way to truly confirm whether chemotherapy improves the results in high-risk MCC. (c) 2006 Elsevier Inc.

Iron (Fe) bioavailability and the distribution of anti-Fe nutrition biochemicals in the unpolished, and bran fraction of five rice gei polished grain riotypes

Iron (Fe) bioavailability in unpolished, polished grain and bran fraction of five rice genotypes with a range of Fe contents was measured by in vitro digestion and cultured Caco-2 cells of cooked grain. There was a significant difference in Fe bioavailability among the five rice genotypes tested, in both the unpolished and polished grain. The range of Fe bioavailability variation in polished rice was much wider than that of unpolished, suggesting the importance of using Fe levels and bioavailability in polished rice grain as the basis for selecting high-Fe rice cultivars for both agronomic and breeding purposes. Milling and polishing the grain to produce polished (or white) rice increased Fe bioavailability in all genotypes. Iron bioavailability in polished rice was high in the UBON2 and Nishiki, intermediate in both IR68144 and KDML105, and low in CMU122. All genotypes had low bioavailability of Fe in bran fraction compared to unpolished and polished grain, except in CMU122. CMU122 contained the lowest level of bioavailable Fe in unpolished and polished grain and bran, because of the dark purple pericarp colored grain and associated tannin content. The level of bioavailable Fe was not significantly correlated with grain Fe concentration or grain phytate levels among these five genotypes tested. The negative relationship between Fe bioavailability and the levels of total extractable phenol was only observed in unpolished (r = -0.83**) and bran fraction (r = -0.50*). The present results suggested that total extractable phenol and tannin contents could also contribute to lowering bioavailability of Fe in rice grain, in addition to phytate. (c) 2006 Society of Chemical Industry

Structural revision of shatavarins I and IV, the major components from the roots of Asparagus racemosus

The two major steroidal saponins from the roots of Asparagus racemosus were isolated by RP-HPLC and their structure determined by extensive NMR studies. Their structures did not match those reported previously for shatavarins. I and IV and were found to be 3-O-{[beta-D-glueopyranosy](1 -> 2)][alpha-L-rhamnopyranosyl(1 -> 4)]-beta-D-glucopyranosyl}-26-O-(P-D-glu(opyranosyl)-(25S)5 beta-furostan-3p,22 alpha,26-triol and 3-O-{[beta-D-glueopyranosyl(1 -> 2)][alpha-L-rhamnopyranosyl(1 -> 4)]-beta-D-glucopyrariosyl}-(25S)-5 beta-spirostan-3 beta-ol. (c) 2006 Elsevier Ltd. All rights reserved.