Novel binding of beryllium to dicarboxyimidazole-based model compounds and polymers

The ligand 4,5-dicarboxyimidazole (H(2)DCI) and its methyl derivative 1-methyl-4,5-dicarboxyimidazole (H(2)MDCI) have been shown to bind to Be(II) forming a zwitterionic species that has been structurally characterized. A new dicarboxyimidazole-based polymer has been prepared and its Be-binding properties have been studied using NMR ((1)H and (9)Be) and fluorescence spectroscopy; it represents a rare example of beryllium binding to a polymer. Models of the mononuclear and polymeric Be(II)-binding sites have been studied using density functional theory (DFT), and the (9)Be NMR chemical shifts of these model materials have been calculated for the purpose of direct comparison to experimentally observed values. Differences in the binding modes of the mononuclear and polymeric species are discussed.     

The application of solid sorbents for the purification of aluminum contaminated chemicals used as modifiers in electrothermal atomic absorption spectrometry

Various microcolumns with solid sorbents (ion exchange resins, functionalised cellulose sorbents, chelating resins) have been tested with respect to their ability for the purification of aluminum contaminated chemicals used as modifiers in electrothermal atomic absorption spectrometry. The purification of NaNO(3), Mg(NO(3))(2), K(2)SO(4) and (NH(4))(2)HPO(4) has been the most effective with an almost 100% efficiency, when Spheron-Oxine was used as chelating resin. The sorption of aluminum from KOH solution has been found to be very high (around 90%) for all investigated sorbents. However, the best results have been obtained with anion-exchange resins. It has been difficult to purify concentrated mineral acids (HCl, H(2)SO(4)). A retention of aluminum above 80% has been achieved only when Cellex P, Chelex 100 or Amberlite XAD-2 have been used.     

D(5h) C50X10: saturn-like fullerene derivatives (X=F, Cl, Br)

Based on the recently reported D(5h) C(50), the geometries and stabilities of its Saturn-like derivatives C(50)X(10) (X=F, Cl, Br) have been investigated by DFT method. Compared with C(50), the equatorial carbon atoms in C(50)X(10) have been saturated by halogens and change to sp(3) hybridization to release the large angle strain. Because the equatorial carbon atoms have been taken out of the pi system by the halogens "ring," the C(50)X(10) system has been split into two well-delocalized conjugated annulene subunits, and then the electronic stabilization has been enhanced.     

Reactivity of sulfur nucleophiles with N-methyl-N-nitroso-p-toluenesulfonamide

The transfer of the nitroso group from N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) to cysteine (CYS) and 2-aminoethanethiol (AET) has been studied in a pH range between pH = 7 and pH = 13. Kinetic results clearly indicate that both nucleophiles react through the corresponding thiolate to give the corresponding nitrosothiol. The existence of two (AET) or three (CYS) macroscopic acidity constants has been kinetically evidenced and the nitrosation rates of the corresponding bases have been identified. Nitrosation rate constants of the different species present in the reaction medium have been determined and a Bronsted-type plot has been established giving a beta(nuc) value approximately equal to 0.08 clearly different from the values of beta(nuc) approximately equal to 0.7 obtained in the nitrosation of primary and secondary amines by MNTS. The low beta(nuc) value has been attributed to the need for previous desolvation of the nucleophile.     

Extraction of gold(III) with (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-yl-methyl)-pentan-3-ol from hydrochloric acid solutions

Extraction of gold(III) with (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)-pentan-3-ol from 3 M hydrochloric acid solutions (with chloroform as a diluent) has been studied. Optimal extraction conditions have been found. The reagent has been shown to extract efficiently metal ion from solutions containing 3 M hydrochloric acid due to formation of coordination bond between gold(III) and the N4 atom of the triazole ring. The coordination mechanism of gold(III) extraction has been proposed on the basis of the data obtained. Concentration constants of extraction have been calculated, and the thermodynamic parameters of extraction have been determined.     

Optimisation and comparison of microwave-assisted extraction and Soxhlet extraction for the determination of polychlorinated biphenyls in soil samples using an experimental design approach

Optimisation of microwave-assisted extraction (MAE) for the extraction of polychlorinated biphenyls (PCBs) from soil samples has been accomplished using an experimental design approach. Variables studied have been: percentage of acetone (v/v) in an acetone:n-hexane mixture, solvent volume, extraction time, microwave power and pressure inside the extraction vessel. Five samples of a certified soil (CRM 481) have been extracted under the optimum conditions of the developed method and the results have been compared to those obtained by Soxhlet extraction. Good recoveries (>95%) have been obtained for all the PCBs studied. All extracts have been analysed by gas chromatography/mass spectrometry (GC/MS) and an optimum determination method for the electron impact mass spectrometric (EIMS) has also been developed.     

Functionalized bis(thiosemicarbazonato) complexes of zinc and copper: synthetic platforms toward site-specific radiopharmaceuticals

Two new types of unsymmetrical bis(thiosemicarbazone) proligands and their neutral zinc(II) and copper(II) complexes have been synthesized. These bifunctional ligands both chelate the metal ions and provide pendent amino groups that can be readily functionalized with biologically active molecules. Functionalization has been demonstrated by the synthesis of three water-soluble glucose conjugates of the new zinc(II) bis(thiosemicarbazonato) complexes, and their copper(II) analogues have been prepared in aqueous solution via transmetalation. A range of techniques including NMR, electron paramagnetic resonance, cyclic voltammetry, high-performance liquid chromatography (HPLC), UV/vis, and fluorescence emission spectroscopy have been used to characterize the complexes. Four compounds, including two zinc(II) complexes, have been characterized by X-ray crystallography. The connectivity and conformation of the glucose conjugates have been assigned by NMR spectroscopy. Time-dependent density functional theory calculations have been used to assign the electronic transitions of the copper(II) bis(thiosemicarbazonato) chromophore. Two copper-64-radiolabeled complexes, including one glucose conjugate, have been prepared and characterized using radio-HPLC, and transmetalation is shown to be a viable method for radiolabeling compounds with copper radionuclides. Preliminary cell washout studies have been performed under normoxic conditions, and the uptake and intracellular distribution have been studied using confocal fluorescence microscopy.     

Bifunctional chelators for copper radiopharmaceuticals: the synthesis of [Cu(ATSM)-amino acid] and [Cu(ATSM)-octreotide] conjugates

Two new bifunctional chelators that are derivatives of the bis(thiosemicarbazone) ATSMH(2) proligand have been prepared, one with two phenyl carboxylate substituents on the exocyclic nitrogens (L(1)H(2)) and one with a single phenyl carboxylate (L(2)H(2)). The new ligands have been characterised by NMR spectroscopy, mass spectrometry and in the case of L(1)H(2) by X-ray crystallography. The copper, nickel and zinc complexes of the new ligands have been synthesised and characterised. Electrochemical measurements show that the copper(II) complexes undergo a reversible reduction attributable to a Cu(II)/Cu(I) process. The new proligands have been tethered to the N-alpha-Boc-protected amino acids lysine and ornithine using solution and solid phase methods. The new amino acid conjugates form copper complexes and the complexes have been characterised by mass spectrometry and electronic spectroscopy. The bifunctional chelator L(2)H(2) has been conjugated to the tumour targeting peptide octreotide and the new ATSMH(2)-octreotide conjugate and its copper complex have been characterized by mass spectrometry. These new systems have the potential to be used for new targeted copper radiopharmaceuticals for imaging and therapy.     

Ring-closing metathesis of chiral allylamines. Enantioselective synthesis of (2S,3R,4S)-3,4-dihydroxyproline

The ring-closing metathesis (RCM) of two types of unsaturated chiral allylamines III, easily available from enantiomerically enriched epoxy alcohols, has been studied. Fully protected allylamines IIIa [(1)R = CH(2)-(CH(2))(n)()-CH=CH(2); (2)R = Boc; (3)R = PMB] have been prepared from unsaturated epoxy alcohols, whereas bis-allylamines IIIb ((1)R = Ph, (2)R = allyl,(3)R = Boc or PMB) have been prepared from 2,3-epoxy-3-phenylpropanol. Both types have been subjected to RCM to provide either cyclic allylamine I or II. The synthetic potential of these intermediates has been demonstrated by the enantioselective synthesis of (2S,3R,4S)-3,4-dihydroxyproline.     

The HCSHSC and HCS+HSC+ systems: molecular properties, isomerization, and energetics

The isomer pair HCSHSC and related cations have been studied by means of a highly accurate level of theory. For all the species investigated the near-equilibrium potential energy surface has been calculated using the coupled cluster method in conjunction with correlation consistent basis sets ranging in size from quadruple to sextuple zeta. After extrapolation to the complete basis set limit, additional corrections due to core-valence correlation and scalar relativistic effects have also been included. Consequently, the molecular and spectroscopic properties as well as the ionization potentials and dissociation energies have been predicted to high accuracy. Isomerization path and energy for both radical and cationic species have also been investigated. Finally, the anharmonic vibrational frequencies have been employed in order to obtain zero-point corrections to ionization potentials, dissociation energies, and isomerization barriers: IP0(HCS) = 7.57(4) eV and IP0(HSC) = 9.00(5) eV; D0(C-H) = 49.29(55) kcal/mol and D0(S-H) = 9.99(37) kcal/mol; deltaE0(HCSHSC) = 39.29(49) kcal/mol, and deltaE0(HCS+HSC+) = 72.24(75) kcal/mol.     

The VUV electronic spectroscopy of acetone studied by synchrotron radiation

The electronic state spectroscopy of acetone (CH3)2CO has been investigated using high-resolution VUV photoabsorption spectroscopy in the energy range 3.7-10.8 eV. New vibronic structure has been observed, notably in the low energy absorption band assigned to the 1(1)A(1) --> 1(1)A2 (ny --> pi*) transition. The local absorption maximum at 7.85 eV has been tentatively attributed to the 4(1)A1 (pi --> pi*) transition. Six Rydberg series converging to the lowest ionisation energy (9.708 eV) have been assigned as well as a newly-resolved ns Rydberg series converging to the first ionic excited state (12.590 eV). Rydberg orbitals of each series have been classified according to the magnitude of the quantum defect (delta) and are extended to higher quantum numbers than in the previous analyses.     

Stability of plutonium(IV) and plutonium(VI) in nitric acid solutions under strong α-irradiation

Plutonium(IV) oxidation has been studied in 1 to 20 mol/1 HNO₃ under 1 to 14 W/1 internal alpha-irradiation and at plutonium concentrations from 2 to 100 mmol/1. Curium isotopes have been used as the basic alpha-irradiation sources. It has been established that in the systems investigated both oxidation of plutonium(IV) and reduction of plutonium(VI) take place, resulting with time in reaching the equilibrium between plutonium(IV) and plutonium(VI). The presence of plutonium(IV) enhances the reduction of plutonium(VI). The rate constants for plutonium(IV) oxidation and plutonium(VI) reduction have been estimated and their dependences upon the concentrations of nitric acid, plutonium(IV) and plutonium(VI) as well as upon the dose rate investigated. An equation has been derived which permits to calculate the concentrations of plutonium(IV) and plutonium(VI) at any desired time.     

Stereochemical elucidation and total synthesis of dihydropacidamycin D, a semisynthetic pacidamycin.

Hydrogenation of the C(4') exocyclic olefin of the pacidamycins has been shown to produce a series of semisynthetic compounds, the dihydropacidamycins, with antimicrobial activity similar to that of the natural products. Elucidation of stereochemistry in the pacidamycins has been completed through a campaign of natural product degradation experiments in combination with the total synthesis of the lowest-molecular weight dihydropacidamycin, dihydropacidamycin D. The stereochemical identities of the tryptophan and two alanine residues contained in pacidamycin D have been shown to be of the natural (S) configuration, and the unique 3-methylamino-2-aminobutyric acid contained in this series of antibiotics has been shown to be of the (2S,3S) configuration. Finally, the stereochemistry obtained by hydrogenation of the C(4')-C(5') exocyclic olefin has been shown to be (R) at the C(4') nucleoside site.     

Luminescent Properties of Europium(III) Complexes with Quinaldic Acid and Sulfur–Containing Neutral Ligands

The luminescent heteroligand complexes of europium(III) with quinaldic acid and sulfur-containing neutral ligands Eu(Quin)3∙D∙3H2O (Quin–quinaldic acid, D–dimethyl sulfoxide or dihexyl sulfoxide) and Eu(Quin)3∙3H2O have been obtained. Their composition and structure have been determined. The thermal and spectral-luminescent properties of the heteroligand europium(III) complexes have been studied. The quinaldate ion has been found to coordinate to the europium(III) ion as a bidentate ligand. The Stark structure of 5D0–7Fj (j = 0, 1, 2) transitions in the low-temperature luminescence spectra of the europium(III) complexes has been analyzed     

Optical, morphological and structural characterization of Langmuir-Schaefer films of a functionalized copper phthalocyanine

Langmuir-Schaefer (LS) films of copper(II) tetrakis-(isoprpoxy-carbonyl)-phthalocyanine (TiPCuPc) have been deposited onto various solid supports. Its floating film have been characterized at the air-water interface by means of Brewster Angle Microscopy and Langmuir curves. Vibrational modes of multilayer transferred LS film have been studied by Raman spectroscopy and the optical parameters (refractive index n and extinction coefficient k) have been determined in the visible range of the electromagnetic spectrum. Linearly polarized light absorbance measurements have been performed at room temperature in the 400-800 nm spectral range and the average orientation of the phthalocyanine rings have been estimated. Transmission electron microscopy has been also used to characterize the morphological properties of the LS film and a close packed arrangement of the deposited molecules has been observed.     

Kinetics and mechanism of the reactions of CH3CO and CH3C(O)CH2 radicals with O2. Low-pressure discharge flow experiments and quantum chemical computations

The reactions CH(3)CO + O(2)--> products (1), CH(3)CO + O(2)--> OH +other products (1b) and CH(3)C(O)CH(2) + O(2)--> products (2) have been studied in isothermal discharge flow reactors with laser induced fluorescence monitoring of OH and CH(3)C(O)CH(2) radicals. The experiments have been performed at overall pressures between 1.33 and 10.91 mbar of helium and 298 +/- 1 K reaction temperature. OH formation has been found to be the dominant reaction channel for CH(3)CO + O(2): the branching ratio, Gamma(1b) = k(1b)/k(1), is close to unity at around 1 mbar, but decreases rapidly with increasing pressure. The rate constant of the overall reaction, k(2), has been found to be pressure dependent: the fall-off behaviour has been analysed in comparison with reported data. Electronic structure calculations have confirmed that at room temperature the reaction of CH(3)C(O)CH(2) with O(2) is essentially a recombination-type process. At high temperatures, the further reactions of the acetonyl-peroxyl adduct may yield OH radicals, but the most probable channel seems to be the O(2)-catalysed keto-enol transformation of acetonyl. Implications of the results for atmospheric modelling studies have been discussed.     

The substrate specificity of the enzyme amyloglucosidase (AMG). Part I. Deoxy derivatives

The eight possible monodeoxy derivatives of methyl beta-maltoside and two bisdeoxy derivatives have been synthesized. The unprotected glycosides have all been investigated by NMR (1H and 13C) spectroscopy in order to confirm their structures and to obtain supporting information about their preferred solution conformations. The compounds have all been tested as substrates toward the hydrolase, amyloglucosidase (AMG) and it has been demonstrated that three hydroxy groups (3, 4' and 6') are essential for the compounds to act as substrate for the enzyme. The kinetic parameters KM (Michaelis-Menten constant) and VM (maximum rate for the reaction) have been determined using 1H NMR spectroscopy at 500 MHz.     

Studies on the Oral Anticancer Drug JM-216: Synthesis and Characterization of Isomers and Related Complexes

The complex cis,trans,cis-[PtCl(2)(OAc)(2)NH(3)(c-C(6)H(11)NH(2))] (JM-216) is currently undergoing clinical evaluation as an antitumor agent. In support of characterization and analysis of this complex a study of its isomers and other complexes [PtCl(m)()(OAc)((4)(-)(m)()())NH(3)(c-C(6)H(11)NH(2))] (m = 0-4) has been undertaken. The complexes have been obtained by a variety of synthetic routes which now extend the scope for the preparation of platinum(IV) antitumor complexes. As platinum(IV) complexes are very stable to substitution in the absence of catalysis, use has been made of both light and base catalysis to promote substitution. Oxidative addition to platinum(II) using hypervalent iodine reagents has also been used. The stereochemistry of the complexes has been confirmed by spectroscopic studies, primarily NMR including natural abundance (15)N NMR spectroscopy.     

Cr(III) and Cr(VI) on-line preconcentration and determination with high performance flow flame emission spectrometry in natural samples

Methods for the on-line chromatographic preconcentration of Cr(III) and Cr(VI) have been developed. Cr(VI) has been preconcentrated on an RP C18 silica based column with tetrabutylammonium-bromide (TBABr) as ion-pairing agent. Specially for Cr(III) a new and effective preconcentration technique based on the sorption of Cr(III)-ions in a C18 column in presence of KH-phthalate has been developed. The efficiency of sample introduction into the atomic emission spectrometer could be improved by hydraulic high pressure nebulization. For the detection of chromium the acetylene/N(2)O flame has been used as a powerful emission spectrometric source. Applying these steps the detection limit (3sigma) could be improved to 25 pg/mL for Cr(III) and to 20 pg/mL for Cr(VI). The method has been applied for the chromium speciation in natural water samples.     

New phytoactive polymers prepared by polycondensation

Some new poly(ether-ester)s (PEEs) and poly(ether-amide)s (PEAs) with polyether sequences linked by tartrate units have been synthesized. Derivatives bearing residues from the synthetic plant-growth regulator 1-naphthylacetic acid (NAA) as pendent groups and end-groups have been prepared by esterification of PEEs and PEAs with NAA. Polymers bearing residues from pyridine-2, 6-dicarboxylic acid (a herbicide) in the main chain have been prepared. The hydrolysis has been found to depend on the structure of the polymer carrier, on pH of the medium and on the ability of the polymers to form complexes with polyacids. The phytosanitary activity of the new polymers has been related to the particular features of their hydrolysis behaviour.