Structural Consequences of S → Se Substitution in some Symmetrical [M(S2CNR2)3] Complexes

The consequences of replacement of the symmetrically chelate ligands in [M(E₂CNR₂)₃] (E = S, Se) complexes of potential 32 symmetry by analogous mixed S,Se unsymmetrical chelates are explored for both small (M = Co) and large (M = In) metal atoms, and R = primary (Et) and secondary (ⁱPr) alkyl substituents by way of low‐temperature single crystal X‐ray studies of [(Co(SSeCNEt₂)₃] ([Co(Se₂CNEt₂)₃] also determined as datum), and [In(SSeCNR₂)₃], R = Et, ⁱPr. The structure of [(ⁱPr₂N·CS·Se)₂] is also recorded.     

The effect of pH on the room-temperature phosphorescence properties of several purine and pyrimidine derivatives

Room-temperature phosphorescence (RTP) spectra of eleven purines and pyrimidines adsorbed on Whatman No. 40 filter paper have been determined in acidic, neutral and basic media. RTP excitation and emission wavelengths do not vary significantly with pH. For most compounds, use of basic (pH approximately 13) solutions yields stronger RTP signals than use of neutral or acidic (pH approximately 1.6) solutions. Exceptions are adenine, theobromine and theophylline, which give larger RTP signals when in neutral than in basic conditions. The existence of differences in phosphorescence quantum yields between the various ionic species as well as of specific pH-related interactions with the substrate is discussed. Absolute limits of detection, ranging between 0.4 and 38 ng for selected compounds, depend on the pH of the analyte solution.     

B-MWW Zeolite: The Case Against Single-Site Catalysis

Boron-containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron-containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B₂(OH)_xO_(3−x/2) (x=0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM-22 isomorphously substituted with boron (B-MWW). Using ¹¹B solid-state NMR spectroscopy, we show that the majority of boron species in B-MWW exist as isolated BO₃ units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B-MWW for ODH of propane falsifies the hypothesis that site-isolated BO₃ units are the active site in boron-based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium-based catalysts and provides an important piece of the mechanistic puzzle.     

On the non-existence of a projective (75, 4,12, 5) set in PG(3, 7)

We show by a combination of theoretical argument and computer search that if a projective (75, 4, 12, 5) set in PG(3, 7) exists then its automorphism group must be trivial. This corresponds to the smallest open case of a coding problem posed by H. Ward in 1998, concerning the possible existence of an infinite family of projective two-weight codes meeting the Griesmer bound.     

Highly sensitive non‐isotopic restriction endonuclease fingerprinting of nucleotide variability in the gp60 gene within Cryptosporidium species,genotypes and subgenotypes infective to humans,and its implications

The high‐resolution analysis of genetic variation has major implications for the identification of parasites and micro‐organisms to species and subspecies as well as for population genetic and epidemiological studies. In this study, we critically assessed the effectiveness of a PCR‐based restriction endonuclease fingerprinting (REF) method for the detection of mutations in the 60 kDa glycoprotein gene (gp60) of Cryptosporidium, a genus of parasitic protists of major human and animal health importance globally. This gene displays substantial intraspecific variability in sequence, particularly in a TCA (perfect and imperfect) microsatellite region, is present as a single copy in the nuclear genome and is used widely as a marker in molecular epidemiological studies of Cryptosporidium hominis and C. parvum, the two predominant species that infect humans. The results of this study demonstrated an exquisite capacity of REF to detect nucleotide variability in the gp60 gene within each of the two species. The differentiation of genotypes/subgenotypes based on REF analysis was supported by targeted sequencing, allowing the detection of levels of variation as low as a single‐nucleotide transversion for amplicons of ∼1 kb in size. The high‐throughput potential and relatively low‐cost of REF make it a particularly useful tool for large‐scale genetic analyses of C. hominis and C. parvum. REF could also be utilized for comparative surveys of genetic variability across large nuclear genomic regions. Such analyses of Cryptosporidium in clinical and environmental samples by REF have important implications for identifying sources of infection, modes of transmission and/or possible infectivity to humans, thus assisting in the surveillance and control of cryptosporidiosis. Given its excellent mutation detection capacity, REF should find broad applicability to various single‐copy genes as well as a wide range of other protozoan and metazoan parasites. (The nucleotide sequences reported in this article are available in the GenBank database under accession numbers GU214343–GU214371).     

A parallel computational method for simulating two‐phase gel dynamics on a staggered grid

We develop a parallel computational algorithm for simulating models of gel dynamics where the gel is described by two phases, a networked polymer and a fluid solvent. The models consist of transport equations for the two phases, two coupled momentum equations, and a volume‐averaged incompressibility constraint. Multigrid with Vanka‐type box‐relaxation scheme is used as preconditioner for the Krylov subspace solver (GMRES) to solve the momentum and incompressibility equations. Through numerical experiments of a model problem, the efficiency, robustness and scalability of the algorithm are illustrated. Copyright © 2008 John Wiley & Sons, Ltd.     

Bounds on some van der Waerden numbers

For positive integers s and k₁,k₂,…,ks, the van der Waerden number w(k₁,k₂,…,ks;s) is the minimum integer n such that for every s-coloring of set {1,2,…,n}, with colors 1,2,…,s, there is a ki-term arithmetic progression of color i for some i. We give an asymptotic lower bound for w(k,m;2) for fixed m. We include a table of values of w(k,3;2) that are very close to this lower bound for m=3. We also give a lower bound for w(k,k,…,k;s) that slightly improves previously-known bounds. Upper bounds for w(k,4;2) and w(4,4,…,4;s) are also provided.