Novel rectangular [Fe4(mu4-OHO)(mu-OH)(2)](7+) versus "butterfly" [Fe4(mu3-O2](8+) core topology in the Fe(III)/RCO2(-)/phen reaction systems (R = Me,Ph; phen = 1,10-phenanthroline): preparation and properties of [Fe4(OHO)(OH)(2)(O2CMe)(4)(phen)(4)](ClO4)(3), [Fe4O2(O2CPh)(7)(phen)(2)](ClO4), and [Fe4O2(O2CPh)(8)(phen)(2)

The preparations, X-ray structures, and detailed physical characterizations are presented for three new tetranuclear Fe(III)/RCO(2)(-)/phen complexes, where phen = 1,10-phenanthroline: [Fe(4)(OHO)(OH)(2)(O(2)CMe)(4)(phen)(4)](ClO(4))(3).4.4MeCN.H(2)O (1.4.4MeCN.H(2)O); [Fe(4)O(2)(O(2)CPh)(7)(phen)(2)](ClO(4)).2MeCN (2.2MeCN); [Fe(4)O(2)(O(2)CPh)(8)(phen)(2)].2H(2)O (3.2H(2)O). Complex 1.4.4MeCN.H(2)O crystallizes in space group P2(1)/n, with a = 18.162(9) A, b = 39.016(19) A, c = 13.054(7) A, beta = 104.29(2) degrees, Z = 4, and V = 8963.7 A(3). Complex 2.2MeCN crystallizes in space group P2(1)/n, with a = 18.532(2) A, b = 35.908(3) A, c = 11.591(1) A, beta = 96.42(1) degrees, Z = 4, and V = 7665(1) A(3). Complex 3.2H(2)O crystallizes in space group I2/a, with a = 18.79(1) A, b = 22.80(1) A, c = 20.74(1) A, beta = 113.21(2) degrees, Z = 4, and V = 8166(1) A(3). The cation of 1 contains the novel [Fe(4)(mu(4)-OHO)(mu-OH)(2)](7+) core. The core structure of 2 and 3 consists of a tetranuclear bis(mu(3)-O) cluster disposed in a "butterfly" arrangement. Magnetic susceptibility data were collected on 1-3 in the 2-300 K range. For the rectangular complex 1, fitting the data to the appropriate theoretical chi(M) vs T expression gave J(1) = -75.4 cm(-1), J(2) = -21.4 cm(-1), and g = 2.0(1), where J(1) and J(2) refer to the Fe(III)O(O(2)CMe)(2)Fe(III) and Fe(III)(OH)Fe(III) pairwise exchange interactions, respectively. The S = 0 ground state of 1 was confirmed by 2 K magnetization data. The data for 2 and 3 reveal a diamagnetic ground state with antiferromagnetic exchange interactions among the four high-spin Fe(III) ions. The exchange coupling constant J(bb) ("body-body" interaction) is indeterminate due to prevailing spin frustration, but the "wing-body" antiferromagnetic interaction (J(wb)) was evaluated to be -77.6 and -65.7 cm(-1) for 2 and 3, respectively, using the appropriate spin Hamiltonian approach. M?ssbauer spectra of 1-3 are consistent with high-spin Fe(III) ions. The data indicated asymmetry of the Fe(4) core of 1 at 80 K, which is not detected at room temperature due to thermal motion of the core. The spectra of 2 and 3 analyze as two quadrupole-split doublets which were assigned to the body and wing-tip pairs of metal ions. (1)H NMR spectra are reported for 1-3 with assignment of the main resonances.     

PTV-LV-GC/MS/MS as screening and complementary method to HRMS for the monitoring of dioxin levels in food and feed

Recent developments in trapping efficiency inside ion trap mass spectrometer permitted to lower instrument detection limit (IDL). An IDL of 200 fg μl⁻¹ injected with a signal-to-noise ratio of 5:1 for tetrachlorodibenzo-p-dioxin (TCDD) was obtained by gas chromatography coupled to a quadrupole ion storage mass spectrometer in tandem mode (GC/MS/MS). Coupling large volume programmable temperature vaporizer (PTV-LV) injection to GC/MS/MS provides an alternative and complementary method to classical splitless-GC injection connected to high-resolution mass spectrometry (splitless-GC/HRMS) method for dioxin monitoring in food and feed.

An injection volume of 10 μl was found to be the best compromise between the sensitivity requirements and the robustness required for a high throughput method. PTV-LV-GC/MS/MS and Splitless-GC/HRMS were compared by performing analysis on five different matrices such as beef fat, yolk eggs, milk powder, animal feed and serum samples covering a concentration range of two orders of magnitude (i.e. 0.2–25 ng WHO-TEQ kg⁻¹). An analysis of variance (ANOVA) was carried out. Fisher tests pointed out that the method effect for all the 2,3,7,8 congeners was not significant, indicating that the null hypothesis (H₀: μ₁=μ₂=…=μ_n) was not rejected. Moreover, the interaction effects between methods and matrices were not significant for most of the 2,3,7,8 congeners. However, three congeners (2,3,7,8-TCDF; 1,2,3,4,7,8-HxCDD and 1,2,3,4,6,7,8-HpCDD) were characterized by P-values lower than the significance level (=0.05). In toxic equivalence (TEQ), the study showed that no significant bias was observed between the two methods. Consequently, PTV-LV-GC/MS/MS is an attractive technique and can be used as a cost effective complementary method to HRMS for dioxin levels monitoring in food and feed.     

Electron-impact fragmentation of the bicyclo[4.1.0]heptane-2-one system: Correlations with photochemistry

The low resolution and complete high resolution mass spectra of a series of methyl and deuterium substituted bicyclo[4.1.0]heptane-2-one derivatives have been measured. An attempt has been made to test the operation of a fragmentation process analogous to the known photochemical rearrangement, and to determine if the substitution effects critical to the photorearrangement also influence the electron-impact process. The fragmentation pattern of these conjugated cyclopropyl ketones is detailed and the influence of the cyclopropyl ring is discussed. It is suggested that electron-impact-induced rearrangements which are analogous to photochemical transformations will be relatively low energy processes and will remain prominent at low ionizing voltages.     

Polycarboxyhydrazides with ferrocenylene groups in the main chain

Polycarboxyhydrazides essentially of the type \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm C}_{10} {\rm H}_8 {\rm Fe}\hbox{---}{\rm CONHNHCO}\rlap{--}]_n $\end{document} are synthesized by low-temperature solution condensation of 1,1′-di(chlorocarbonyl) ferrocene with hydrazine or 1, 1′-ferrocenedicarboxyhydrazide and hexamethylphosphoramide as solvent. In an analogous manner the polycondensation of 1, 1′-di(chlorocarbonyl)ferrocene with oxalyldihydrazide leads to polyhydrazides essentially possessing the structure \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm C}_{10} {\rm H}_8 {\rm Fe}\hbox{---}{\rm CONHNHCO}\hbox{---}{\rm CONHNHCO}\rlap{--}]_n $\end{document}. Both polymer types exhibit inherent viscosities (0.08–0.19 dl./g.) considerably lower than reported for analogous aliphatic or benzene-aromatic polyhydrazides. This behavior points to premature chain termination via heterobridging imide groups as a result of the welldocumented tendency of appropriately substituted ferrocene compounds to undergo intramolecular cyclization. In addition, elemental analytical and spectroscopic evidence, coupled with the failure of both polymer types to undergo cyclodehydration to the corresponding 1,3,4-oxadiazole polymers upon heat treatment, suggests some structural irregularities in the aliphatic connecting segments arising from ferrocenoylation of secondary amino groups with resultant branching. With the polyhydrazide prepared from 1, 1′-di(chlorocarbonyl)ferrocene and 1, 1′-ferrocenedicarboxyhydrazide it is shown spectroscopically that treatment with alkali results in conversation of the nonconjugated hydrazide structure of the connecting segments into the polyconjugated tautomeric enol form comprising azine groups.     

Determination of (1)H homonuclear scalar couplings in unlabeled carbohydrates

The scarcity of structural information on carbohydrates results from combined difficulties to crystallize and the limitations in NMR analysis. Current methods for determining basic NMR parameters such as (1)H homonuclear scalar couplings are very limited, especially for large molecules such as polysaccharides, oligonucleotides, and the carbohydrate part of glycoproteins. In this paper, a NMR experiment for the determination of endocyclic (1)H homonuclear scalar couplings ((3)J(HH)) in unlabeled carbohydrates is presented. In addition to scalar couplings, cross-correlated dipole-dipole relaxation rates were measured for large polysaccharides. The measurement of all endocyclic homonuclear coupling constants within monosaccharide units is presented for lactose, a model disaccharide, and for a natural-abundance 2 MDa bacterial polysaccharide excreted by Streptococcus thermophilus Sfi39.     

A cationic 24-MC-8 manganese cluster with ring metals possessing three oxidation states [Mn(II)4Mn(III)6Mn(IV)2(mu4-O)2(mu3-O)4(mu3-OH)4(mu3-OCH3)2(pko)12](OH)(ClO4)3

Reaction of Mn(ClO4)2 with di-pyridyl ketone oxime, (2-py)2C=NOH, gives the novel cluster [Mn(II)4Mn(III)6Mn(IV)2(mu4-O)2(mu3-O)4(mu3-OH)4(mu3-OCH3)2(pko)12](OH)(ClO4)3 1. It is the only example of a 24-MC-8, and the first metallacrown with ring metal ions in three different oxidation states. Magnetic measurements show antiferromagnetic behavior.     

Dynamic behavior of DNA base pairs containing 8-oxoguanine

The process by which DNA repair enzymes recognize and selectively excise damaged bases in duplex DNA is fundamental to our mechanistic understanding of these critical biological reactions. 8-Oxoguanine (8-oxoG) is the most common form of oxidative DNA damage; unrepaired, this lesion generates a G:C-->T:A mutation. Central to the recognition and repair of DNA damage is base extrusion, a process in which the damaged base lesion or, in some cases, its partner disengages from the helix and is bound to the enzyme's active site where base excision takes place. The conformation adopted by 8-oxoG in duplex DNA is affected by the base positioned opposite this lesion; conformational changes may also take place when the damaged base binds to its cognate repair enzyme. We performed unrestrained molecular dynamics simulations for several 13-mer DNA duplexes. Oligomers containing G:C and 8oxoG:C pairs adopted Watson-Crick geometries in stable B-form duplexes; 8oxoG showed increased local and global flexibility and a reduced barrier to base extrusion. Duplexes containing the G:A mismatch showed much larger structural fluctuations and failed to adopt a well-defined structure. For the 8oxoG:A mismatch that is recognized by the DNA glycosylase MutY, the damaged nucleoside underwent spontaneous and reproducible anti-->syn transitions. The syn conformation is thermodynamically preferred. Steric hindrance and unfavorable electrostatics associated with the 8oxoG O8 atom in the anti conformation were the major driving forces for this transition. Transition events follow two qualitatively different pathways. The overall anti-->syn transition rate and relative probability of the two transition paths were dependent on local sequence context. These simulations indicate that both the dynamic and equilibrium behavior of the duplex change as a result of oxidation; these differences may provide valuable new insight into the selective action of enzymes on damaged DNA.     

Water-soluble calix[4]resorcarenes as enantioselective NMR shift reagents for aromatic compounds

A tetra L-prolinylmethyl derivative of a tetra-sulfonated calix[4]resorcarene (1) is an effective chiral NMR solvating agent for water-soluble compounds with phenyl, pyridyl, bicyclic aromatic, or indole rings. These aromatic compounds form host-guest complexes with the calix[4]resorcarene in water. Complexation of substrates with the calix[4]resorcarene is likely promoted by hydrophobic effects, and bicyclic substrates have association constants with the calix[4]resorcarene larger than those of similar phenyl-containing compounds. Aromatic resonances of the substrates show substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcarene, and several resonances in the 1H NMR spectra typically exhibit enantiomeric discrimination. The extent of enantiomeric discrimination depends in part on interactions of the substituent groups of the substrates with the prolinylmethyl groups of the calix[4]resorcarene. The effectiveness of a calix[4]resorcarene prepared from N-methyl-L-alanine (2) as a chiral NMR discriminating agent is compared to the L-prolinylmethyl derivative.     

Quadrupole mass spectrometric study of positive ions from RF plasmas of pure CH4, CH4/H2, and CH4/Ar systems

Quadrupole mass spectrometry has been employed to characterize the ionic species in the discharges of pure CH₄, CH₄/H₂, and CH₄/Ar systems. For pure methane, the major positive ions in the discharge at low pressure (e.g., 0.15 torr) are CH ₃ ⁺ , C₂H ₃ ⁺ , CH ₂ ⁺ , C₂H ₂ ⁺ , CH ₄ ⁺ , C₂H ₄ ⁺ , and C₂H ₅ ⁺ at high pressure (e.g., 0.5 torr) the major ions are CH ₃ ⁺ , C₂H ₃ ⁺ , C₂H ₅ ⁺ , C₃H ₃ ⁺ , C H₃H ₇ ⁺ , C₄H ₇ ⁺ , C₅H ₇ ⁺ , C₆H ₅ ⁺ , and C₇H ₇ ⁺ . The relative abundances of C₁ ions decrease with increasing pressure, whereas those of higher-order ions increase with pressure. For 5% CH₄ + 95% H₂ mixture, in addition to those sampling from the pure methane plasma at the lower pressure, H _n ⁺ ions have also been detected. For 5% CH₄ +95% Ar mixture, the principal ions are CH ₃ ⁺ , CH ₂ ⁺ , CH⁺, CH ₅ ⁺ , Ar⁺, and ArH⁺; the ions containing more than two carbon atoms are negligible. In these discharges, the CH ₃ ⁺ and C₂H ₃ ⁺ are the most important positive ions in C₁ and C₂ ions, respectively. The ions detected are believed to come from the sheath between the electrode and the luminous plasma, and have high kinetic energy. An ion-molecule reaction mechanism is proposed which can well explain the observed main features of ionic products.Died June 1, 1991.     

Triiron and Triruthenium Carbonyl Clusters Bearing Bridging Long Chain Diphosphine and Capping Chalcogenido Ligands

Treatment of Ru₃(CO)₁₂ with dpphSe₂ (dpph = 1,6-bis(diphenylphosphino)hexane) in refluxing toluene in the presence of Me₃NO afforded two new compounds, Ru₃(CO)₇(-CO)(₃-Se)(-dpph) (1) and Ru₃(CO)₇(₃-Se)₂(-dpph) (2). A similar reaction of Ru₃(CO)₁₂ with dpppeSe₂ (dpppe = 1,5-bis(diphenylphosphino)pentane) gave exclusively Ru₃(CO)₇(₃-Se)₂(-dpppe) (3). Treatment of Ru₃(CO)₁₂ with dpphS₂ and dpppeS₂ at 110°C in the presence of Me₃NO afforded Ru₃(CO)₇(₃-S)₂(-dpph) (4) and Ru₃(CO)₇(₃-S)₂(-dpppe) (5), respectively. Reactions of Fe₃(CO)₁₂ with dpphSe₂ and dpppeSe₂, under identical conditions, afforded Fe₃(CO)₇(₃-Se)₂(-dpph) (6) and Fe₃(CO)₇(₃-Se)₂(-dpppe) (7), respectively. Compounds 1–7 were characterized spectroscopically and the molecular structures of compounds 1–4 were determined by single crystal X-ray crystallography. The core of 1 contains an equilateral triangle of ruthenium atoms with one capping selenium, one bridging dpph, one doubly bridging carbonyl and seven terminal carbonyl ligands. Complexes 2–4 have a square-pyramidal structure with two metal and two chalcogenide atoms alternating in the basal plane and the third metal atom at the apex of the pyramid, and belong to the family of well-known nido clusters with seven skeletal electron pairs.