Preconcentration of trace lead via formation of the bis(2,2-bipyridyl) complex and its adsorption on oxidized multiwalled carbon nanotubes

A solid phase extraction method is presented for the preconcentration of trace lead ions on oxidized multiwalled carbon nanotubes (ox-MWCNTs). In the first step, the cationic Pb(II) complex of 2,2-bipyridyl is formed which, in a second step, is adsorbed on ox-MWCNTs mainly due to electrostatic and van der Waals interactions. The Pb(II) ions were then eluted with dilute nitric acid and quantified by FAAS. The effects of pH value, mass of sorbent, concentration of 2,2-bipyridyl, stirring time, of type, concentration and volume of eluent, of eluent flow rate and sample volume were examined. Most other ions do not affect the recovery of Pb(II). The limits of detection are 240 and 60 ng L^?1 for sample volumes of 100 and 400 mL, respectively. The recovery and relative standard deviation are >95 % and 2.4 %, respectively. Other figures of merit include a preconcentration factor of 160 and a maximum adsorption capacity of 165 mg g^?1. The method was successfully applied to the determination of Pb(II) in spiked tap water samples. The accuracy of the method was verified by correctly analyzing a certified reference material (NCS ZC85006; lead in tomatoes).

M/M/1 Queueing systems with inventory

We derive stationary distributions of joint queue length and inventory processes in explicit product form for various M/M/1-systems with inventory under continuous review and different inventory management policies, and with lost sales. Demand is Poisson, service times and lead times are exponentially distributed. These distributions are used to calculate performance measures of the respective systems. In case of infinite waiting room the key result is that the limiting distributions of the queue length processes are the same as in the classical M/M/1/∞-system. All authors were supported by DAAD/KBN grant number D/02/32206.     

A catalogue of small maximal nonhamiltonian graphs

In this paper a catalogue of all maximal nonhamiltonian graphs of orders up to 10 is provided. Special attention is paid to maximal nonhamiltonian graphs with non-positive scattering number since all remaining ones (with scattering number 1) are fully characterized and counted by the third author. We also give a sketch of the method used to produce the catalogue.     

A Unified Treatment of the Relationship Between Ligand Substituents and Spin State in a Family of Iron(II) Complexes

The influence of ligands on the spin state of a metal ion is of central importance for bioinorganic chemistry, and the production of base‐metal catalysts for synthesis applications. Complexes derived from [Fe(bpp)₂]²⁺ (bpp=2,6‐di{pyrazol‐1‐yl}pyridine) can be high‐spin, low‐spin, or spin‐crossover (SCO) active depending on the ligand substituents. Plots of the SCO midpoint temperature (T ) in solution vs. the relevant Hammett parameter show that the low‐spin state of the complex is stabilized by electron‐withdrawing pyridyl (“X”) substituents, but also by electron‐donating pyrazolyl (“Y”) substituents. Moreover, when a subset of complexes with halogeno X or Y substituents is considered, the two sets of compounds instead show identical trends of a small reduction in T for increasing substituent electronegativity. DFT calculations reproduce these disparate trends, which arise from competing influences of pyridyl and pyrazolyl ligand substituents on Fe‐L σ and π bonding.     

A nickel hydride complex in the active site of methyl-coenzyme m reductase: implications for the catalytic cycle

Methanogenic archaea utilize a specific pathway in their metabolism, converting C1 substrates (i.e., CO2) or acetate to methane and thereby providing energy for the cell. Methyl-coenzyme M reductase (MCR) catalyzes the key step in the process, namely methyl-coenzyme M (CH3-S-CoM) plus coenzyme B (HS-CoB) to methane and CoM-S-S-CoB. The active site of MCR contains the nickel porphinoid F430. We report here on the coordinated ligands of the two paramagnetic MCR red2 states, induced when HS-CoM (a reversible competitive inhibitor) and the second substrate HS-CoB or its analogue CH3-S-CoB are added to the enzyme in the active MCR red1 state (Ni(I)F430). Continuous wave and pulse EPR spectroscopy are used to show that the MCR red2a state exhibits a very large proton hyperfine interaction with principal values A((1)H) = [-43,-42,-5] MHz and thus represents formally a Ni(III)F430 hydride complex formed by oxidative addition to Ni(I). In view of the known ability of nickel hydrides to activate methane, and the growing body of evidence for the involvement of MCR in "reverse" methanogenesis (anaerobic oxidation of methane), we believe that the nickel hydride complex reported here could play a key role in helping to understand both the mechanism of "reverse" and "forward" methanogenesis.     

"Two-point" assembling of Zn(II) and Co(II) metalloporphyrins derivatized with a crown ether substituent in Langmuir and Langmuir-Blodgett films

The effect of "two-point" interactions of Zn(II) and Co(II) metalloporphyrins, bearing 15-crown-5 ether peripheral substituents, on their assembling in Langmuir and Langmuir-Blodgett (LB) films was investigated. That is, simultaneously, the central metal ion of the porphyrin was axially ligated by a nitrogen-containing ligand in the emerged part of the Langmuir film on one hand, and a suitably selected cation pertaining in the subphase solution was supramolecularly complexed by the crown ether moiety in the submerged part of the film on the other. The compression and polarity properties of the Langmuir films of the derivatized free-base 5,10,15-triphenyl-20-(benzo-15-crown-5)porphyrin, H2(TPMCP), and the corresponding cobalt(II) and zinc(II) metalloporphyrins, denoted as Co(TPMCP) and Zn(TPCMP), respectively, as well as inclusion complexes of the metalloporphyrins with selected cations were investigated. For the axial ligation of Zn(II) and Co(II), pyrazine (pyz) and 4,4'-bipyridnine (bpy) aromatic as well as piperazine (ppz) and 1,4-diazabicyclo[2.2.2]octane (DABCO) cyclic heteroaliphatic ligands were selected. The films were formed on the water subphase solution in the absence and presence of LiCl, NaCl, or NH4Cl. The Langmuir films were built of monolayer J-type aggregates of tilted porphyrin macrocycles. The porphyrins formed rather labile complexes with the cations in the subphase. Nevertheless, the XPS analysis revealed that these cations were LB transferred together with the porphyrins onto solid substrates. In the Co(TPMCP) Langmuir films formed on the water subphases, Co(II) was complexed by aromatic but not cyclic heteroaliphatic ligands, while, in these films formed on the NaCl subphase solutions, the metalloporphyrin was also complexed by DABCO. In Langmuir films spread on alkaline subphase solutions, both aromatic and heteroaliphatic ligands formed complexes with Co(TPMCP) of different stoichiometries. The X-ray reflectivity and GIXD measurements performed on selected LB films revealed some structure-building effects of the axial ligation.     

Multilevel surface nano- and microstructuring via sequential photoswelling of dichromated gelatin

Photoswelling of thin films of dichromated gelatin provides a basis for fabrication of multilevel surface reliefs via sequential UV illumination through different photomasks. The remarkable feature of this simple, benchtop technique is that by adjusting irradiation times, film thickness, or its hydration state the heights of the developed features can be varied from few nanometers to tens of microns. After UV exposure, the surface structures can be replicated faithfully into either soft or hard PDMS stamps.     

Characterization of 2-methylglyceric acid oligomers in secondary organic aerosol formed from the photooxidation of isoprene using trimethylsilylation and gas chromatography/ion trap mass spectrometry

In the present work, we have characterized in detail the chemical structures of secondary organic aerosol (SOA) components that were generated in a smog chamber and result from the photooxidation of isoprene under high-NO(x) conditions typical for a polluted atmosphere. Isoprene high-NO(x) SOA contains 2-methylglyceric acid (2-MG) and oligoester derivatives thereof. Trimethylsilylation, in combination with capillary gas chromatography (GC)/ion trap mass spectrometry (MS) and detailed interpretation of the MS data, allowed structural characterization the polar oxygenated compounds present in isoprene SOA up to 2-MG trimers. GC separation was achieved between 2-MG linear and branched dimers or trimers, as well as between the 2-MG linear dimer and isomeric mono-acetate derivatives thereof. The electron ionization (EI) spectra of the trimethylsilyl derivatives contain a wealth of structural information, including information about the molecular weight (MW), oligoester linkages, terminal carboxylic and hydroxymethyl groups, and esterification sites. Only part of this information can be achieved with a soft ionization technique such as electrospray (ESI) in combination with collision-induced dissociation (CID). The methane chemical ionization (CI) data were used to obtain supporting MW information. Interesting EI spectral differences were observed between the trimethylsilyl derivatives of 2-MG linear and branched dimers or trimers and between 2-MG linear dimer mono-acetate isomers.     

Banach-Mazur Distances and Projections on Random Subgaussian Polytopes

We consider polytopes in that are generated by N vectors in whose coordinates are independent subgaussian random variables. (A particular case of such polytopes are symmetric random polytopes generated by N independent vertices of the unit cube.) We show that for a random pair of such polytopes the Banach-Mazur distance between them is essentially of a maximal order n. This result is an analogue of the well-known Gluskin's result for spherical vectors. We also study the norms of projections on such polytopes and prove an analogue of Gluskin's and Szarek's results on basis constants. The proofs are based on a version of "small ball" estimates for linear images of random subgaussian vectors.     

Interactions between short-term and long-term cardiovascular control mechanisms

The cardiovascular system incorporates several controlling mechanisms acting as feedback loops over different time horizons. Because of their complex interrelationships, information-based methods such as autonomic information flow (AIF) functions promise to be useful in identifying normal and pathological behavior. Optimal adjustment between those controllers is necessary for healthy global behavior of the organism. We investigated the question as to whether there are typical relationships between short-term and long-term AIF by means of a meta-analysis of several of our own clinical studies of the mortality of patients with multiple organ dysfunction syndrome, heart failure, idiopathic dilated cardiomyopathy, and the length of stay in hospital after abdominal aorta surgery. We found a fundamental association of increased short-term randomness (decreased AIF) and decreased long-term randomness (increased AIF) due to pathology. A systems theoretic validation of this fundamental type of association was done by an appropriate mathematical model using a dissipative system with two feedback loops over different time horizons. The systematic simulation of an increasing collapse of the short feedback loop confirmed the inverse association between short-term and long-term information flow as a fundamental, system inherent type of readjustment that occurs under pathological conditions.