Synthesis and Characterization of [(1,4‐diamine)dichloro]platinum(II) Compounds Preliminary Studies on their Biological Activity

Two 1,4‐diamine ligands were synthesized having 1,2‐bis(aminomethyl)‐cyclohexane and 1,2‐bis(aminomethyl)‐benzene structures. The two ligands have different electron density in the six‐membered ring: a cyclohexane versus a phenyl ring. The organic synthesis of the ligands was carried out by synthetic pathways of seven and four steps, respectively, starting from 1,2,3,6‐tetrahydrophthalic anhydride and diethyl phthalate. The coordination of platinum to these ligands afforded platinum(II) complexes which are analogue to the clinical drug cisplatin but form a seven‐membered chelate ring. The interaction of the platinum compounds with DNA was studied in order to know the relationship between the electron density of ligands and their capability to chelate DNA, by using three techniques: Circular Dichroism, Agarose Gel Electrophoresis and Atomic Force Microscopy. The degree of interaction of both compounds with DNA was slightly different, but both complexes showed a cisplatin‐like behaviour and are promising candidates to follow an extensive study of their cytotoxic activity.     

Analysis of Toxic Aluminium Species in Natural Waters

Aluminium is known to be toxic to a wide range of aquatic organisms under certain conditions. Monomeric hydroxy ions have been found to be primarily responsible for aluminium aquatic toxicity.A survey of aluminium toxicity and a brief discussion of speciation schemes are presented. The fast reaction of Al³⁺ with pyrocatechol violet (PCV) followed by spectrophotometric analysis is a frequently used method for aluminium speciation. By using a flow system, one obtains fairly exact and reproducible control of the reaction time, and as a result it provides a direct method of analysis for free aluminium (including inorganic monomeric aluminium).The PCV-method has been adapted for the determination of aluminium in carbonate-rich natural waters using an improved buffering system. Thus it is possible to monitor aluminium concentrations in lake water as well as in pore water of the sediments of eutrophicated hardwater lakes that has been treated with aluminium salts as a restoration measure.     

Generation of new landomycins by combinatorial biosynthetic manipulation of the LndGT4 gene of the landomycin E cluster in S. globisporus

A 3 kb DNA fragment from the Streptomyces globisporus 1912 landomycin E (LaE) biosynthetic gene cluster (lnd) was completely sequenced. Three open reading frames were identified, lndGT4, lndZ4, and lndZ5, whose probable translation products resemble a glycosyltransferase, a reductase, and a hydroxylase, respectively. Studies of generated mutants from disruption and complementation experiments involving the lndGT4 gene allowed us to determine that LndGT4 controls the terminal L-rhodinose sugar attachment during LaE biosynthesis and that LndZ4/LndZ5 are responsible for the unique C11-hydroxylation of the landomycins. Generation of the novel landomycins F, G, and H in the course of these studies provided evidence for the flexibility of lnd glycosyltransferases toward their acceptor substrates and a basis for initial structure-activity relationships within the landomycin family of antibiotics.     

Spectrophotometric and derivative spectrophotometric determination of aluminium with Hydroxynaphthol Blue

The reaction of aluminium(III) with Hydroxynaphtol Blue (HNB) in aqueous media at apparent pH 5.5 results in a red complex that is stable for at least 4 hr. Beer's Law is obeyed up to 1.6 microg/ml of aluminium(III) with an apparent molar absorptivity of 1.66 x 10(4) l.mol(-1). cm(-1) at 569 nm. This paper proposes procedures for aluminium(III) determination by ordinary and first-derivative spectrophotometry. The results demonstrated that the linear dynamic range is 0.03-1.60 microg/ml for ordinary spectrophotometry and 11.8-320.0 ng/ml for first derivative spectrophotometry. The HNB is not selectivity for aluminium, but the addition of EDTA allows the aluminium determination in the presence of accepted amounts of Ca(II), Mg(II), Mn(II), Ba(II), Sr(II), Cd(II), Pb(II), La(III), In(III), Bi(III) and Zn(II). The interference of Cu(II) and Hg(II) can be masked by thiosulphate. Ions such as UO(2)(II), Mo(VI), Co(II), Ti(IV) and PO(4)(III) do interfere seriously. This method was applied for aluminium determination in copper-base alloy, zinc-base alloy, magnesium-base alloy, iron ore, manganese ore, cement, dolomite, feldspar and limestone. The results indicated high accuracy and precision.     

Analysis of nickel-niobium alloys by inductively coupled plasma optical emission spectrometry

Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO₃. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%.     

Direct determination of selenium in urine samples by electrothermal atomic absorption spectrometry using a Zr plus Rh-treated graphite tube and co-injection of Rh as chemical modifier

Different chemical modifiers for use with electrothermal atomic absorption spectrometry (ET AAS) were investigated in relation to determining the selenium in human urine samples. The samples were diluted in a solution containing 1% v/v HNO₃ and 0.02% m/v cetyltrimethylammonium chloride (CTAC). Studying the modifiers showed that the use of either Ru or Ir as the permanent modifier gave low sensitivity to Se and the peak shape was very noisy, while Zr or Rh gave no peak at all. The same occurred when Zr was used in solution. For mixtures of permanent modifiers, Ir plus Rh or Zr plus Rh gave very low sensitivity, Zr plus Rh with co-injection of Ir in solution was also not efficient, Zr plus Rh in solution gave good sensitivity, but the best results were obtained with a mixture of Zr and Rh as the permanent modifier and co-injection of Rh in solution. Using this last modifier, the following dilutions with the HNO₃ and CTAC were studied: 1:1, 1:2, 1:3 and 1:4. The best dilution was 1:1, which promoted good sensitivity and a more defined peak shape and made it possible to correct for the background using a deuterium arc lamp. Under these conditions, a characteristic mass of 26±0.2 pg was obtained for Se in aqueous solution. Six certified urine samples were analyzed using matrix matching calibration and the measured concentrations were in agreement with the certified values, according to a t-test at the 95% confidence level. Recovery tests were carried out and the recoveries were in the range 100–103%, with relative standard deviation better than 9%. The limit of detection (LOD, 3 sd, n=10) was 3.0 μg L⁻¹ in the sample. The treated graphite tube could be used for at least 600 atomization cycles without significant alteration of the analytical signal.     

Hierarchical assembly of helicate-type dinuclear titanium(IV) complexes

The ligands 4-7-H(2) were used in coordination studies with titanium(IV) and gallium(III) ions to obtain dimeric complexes Li(4)[(4-7)(6)Ti(2)] and Li(6)[(4/5a)(6)Ga(2)]. The X-ray crystal structures of Li(4)[(4)(6)Ti(2)], Li(4)[(5b)(6)Ti(2)], and Li(4)[(7a)(6)Ti(2)] could be obtained. While these complexes are triply lithium-bridged dimers in the solid state, a monomer/dimer equilibrium is observed in solution by NMR spectroscopy and ESI FT-ICR MS. The stability of the dimer is enhanced by high negative charges (Ti(IV) versus Ga(III)) of the monomers, when the carbonyl units are good donors (aldehydes versus ketones and esters), when the solvent does not efficiently solvate the bridging lithium ions (DMSO versus acetone), and when sterical hindrance is minimized (methyl versus primary and secondary carbon substituents). The dimer is thermodynamically favored by enthalpy as well as entropy. ESI FT-ICR mass spectrometry provides detailed insight into the mechanisms with which monomeric triscatecholate complexes as well as single catechol ligands exchange in the dimers. Tandem mass spectrometric experiments in the gas phase show the dimers to decompose either in a symmetric (Ti) or in an unsymmetric (Ga) fashion when collisionally activated. The differences between the Ti and Ga complexes can be attributed to different electronic properties and a charge-controlled reactivity of the ions in the gas phase. The complexes represent an excellent example for hierarchical self-assembly, in which two different noncovalent interactions of well balanced strengths bring together eleven individual components into one well-defined aggregate.     

Electron transfer in proteins: nonorthogonal projections onto donor-acceptor subspace of the Hilbert space

We develop nonorthogonal projectors, called L?wdin projectors, to construct an effective donor-acceptor system composed of localized donor (D) and acceptor (A) states of a long-distance electron transfer problem. When these states have a nonvanishing overlap with the bridge states these projectors are non-Hermitian and there are various possible effective two-level systems that can be built. We show how these can be constructed directly from the Schr?dinger or Dyson equation projected onto the D-A subspace of the Hilbert space and explore these equations to determine the connection between Hamiltonian and Green function partitioning. We illustrate the use of these effective two-level systems in estimating the electron transfer rate in the context of a simple electron transfer model.