Mixed covering arrays on graphs

Covering arrays have applications in software, network and circuit testing. In this article, we consider a generalization of covering arrays that allows mixed alphabet sizes as well as a graph structure that specifies the pairwise interactions that need to be tested. Let k and n be positive integers, and let G be a graph with k vertices v₁,v₂,…, v_k with respective vertex weights g₁ ≤ g₂ ≤ … ≤ g_k. A mixed covering array on G, denoted by , is an n × k array such that column i corresponds to v_i, cells in column i are filled with elements from ?_gi and every pair of columns i,j corresponding to an edge v_i,v_j in G has every possible pair from ?_gi × ?_gj appearing in some row. The number of rows in such array is called its size. Given a weighted graph G, a mixed covering array on G with minimum size is called optimal. In this article, we give upper and lower bounds on the size of mixed covering arrays on graphs based on graph homomorphisms. We provide constructions for covering arrays on graphs based on basic graph operations. In particular, we construct optimal mixed covering arrays on trees, cycles and bipartite graphs; the constructed optimal objects have the additional property of being nearly point balanced. © 2007 Wiley Periodicals, Inc. J Combin Designs 15: 393–404, 2007     

Nanoscale indentation of polymer and composite polymer-silica core-shell submicrometer particles by atomic force microscopy

Atomic force microscopy was employed to probe the mechanical properties of surface-charged polymethylmethacrylate (PMMA)-based terpolymer and composite terpolymer core-silica shell particles in air and water media. The composite particles were achieved with two different approaches: using a silane coupling agent (composite A) or attractive electrostatic interactions (composite B) between the core and the shell. Young's moduli (E) of 4.3+/-0.7, 11.1+/-1.7, and 8.4+/-1.7 GPa were measured in air for the PMMA-based terpolymer, composite A, and composite B, respectively. In water, E decreases to 1.6+/-0.2 GPa for the terpolymer; it shows a slight decrease to 8.0+/-1.2 GPa for composite A, while it decreases to 2.9+/-0.6 GPa for composite B. This trend is explained by considering a 50% swelling of the polymer in water confirmed by dynamic light scattering. Close agreement is found between the absolute values of elastic moduli determined by nanoindentation and known values for the corresponding bulk materials. The thickness of the silica coating affects the mechanical properties of composite A. In the case of composite B, because the silica shell consists of separate particles free to move in the longitudinal direction that do not individually deform when the entire composite deforms, the elastic properties of the composites are determined exclusively by the properties of the polymer core. These results provide a basis for tailoring the mechanical properties of polymer and composite particles in air and in solution, essential in the design of next-generation abrasive schemes for several technological applications.     

Resatorvid‐based Pharmacological Antagonism of Cutaneous TLR4 Blocks UV‐induced NF‐κB and AP‐1 Signaling in Keratinocytes and Mouse Skin

Cutaneous exposure to solar ultraviolet (UV) radiation is a major causative factor in skin carcinogenesis, and improved molecular strategies for efficacious chemoprevention of nonmelanoma skin cancer (NMSC) are urgently needed. Toll‐like receptor 4 (TLR4) signaling has been shown to drive skin inflammation, photoimmunosuppression, and chemical carcinogenesis. Here we have examined the feasibility of genetic and pharmacological antagonism targeting cutaneous TLR4 for the suppression of UV‐induced NF‐κB and AP‐1 signaling in keratinocytes and mouse skin. Using immunohistochemical and proteomic microarray analysis of human skin, we demonstrate for the first time that a significant increase in expression of TLR4 occurs in keratinocytes during the progression from normal skin to actinic keratosis, also detectible during further progression to squamous cell carcinoma. Next, we demonstrate that siRNA‐based genetic TLR4 inhibition blocks UV‐induced stress signaling in cultured keratinocytes. Importantly, we observed that resatorvid (TAK‐242), a molecularly targeted clinical TLR4 antagonist, blocks UV‐induced NF‐κB and MAP kinase/AP‐1 activity and cytokine expression (Il‐6, Il‐8, and Il‐10) in cultured keratinocytes and in topically treated murine skin. Taken together, our data reveal that pharmacological TLR4 antagonism can suppress UV‐induced cutaneous signaling, and future experiments will explore the potential of TLR4‐directed strategies for prevention of NMSC.     

Preservation of non-covalent associations in electrospray ionization mass spectrometry: Multiply charged polypeptide and protein dimers

The ‘softness’ of the electrospray ionization (ESI) method provides a direct link between solution chemistry and the inherent gas-phase environment of mass Spectrometry. Available results related to the preservation of non-covalent associations into the gas phase after ESI are reviewed. These associations include the possible retention of elements of higher order protein structure, non-covalent polypeptide–heme associations and enzyme complexes. Experimental results are presented showing that non-covalently bound polypeptide and protein dimer ions are relatively common as low level contributions to ESI mass spectra. It is argued that these dimers are reflective of multimeric species in solution since Coulombic barriers preclude dimerization after ESI although uncertainty remains regarding whether they exist prior to the formation of highly charged droplets. The dissociation of dimers is facile and for proteins can yield monomers having a broad distribution of charge states. The detection of non-covalently associated dimers requires gentle ESI mass spectrometer interface conditions, yielding relatively low levels of internal excitation. Under such conditions incomplete molecular ion desolvation can result in experimental artifacts for tandem mass spectrometric experiments. ESI mass Spectrometry may have broad potential for the study of noncovalent liquid phase associations.     

Rate constant for the reaction of Cl with CHCl3

The rate constant for the reaction of Cl with CHCl₃ was measured relative to the Cl reaction with CH₄ and CH₃Cl using long path FTIR. The measured rate constant at 298 K and 1 atm total pressure was (1.21 ± 0.13) × 10⁻¹³ cm³ molecule ⁻¹s⁻¹ (2σ) about 60% larger than the currently recommended value (although within the large error bars). The implications of the Cl + CHCl₃ reaction for relative rate studies chloromethane reactivity, and tropospheric chemistry are discussed. © 1996 John Wiley & Sons, Inc.     

Mass spectrometry in structural and stereochemical problems—CLXXVIII: The electron-impact promoted fragmentation of 1,2-cyclohexene oxide

The mass spectra of 1,2-cyclohexene oxide and three deuterium labeled analogs are discussed and mechanistic rationalizations are given for the major fragmentation processes observed. Multiple mechanisms are required to explain the indicated peak shifts in the labeled analogs for many of these ions, thus demonstrating again the care that needs to be exercised in the interpretation of the mass spectra of relatively simple molecules.     

Synthesis of l-arabinopyranose containing hederagenin saponins

The synthesis of eight hederagenin saponins, five of which are natural products, and their methyl esters is described as part of an ongoing study of the biological activity of triterpenoid saponins. Six disaccharides consisting of an l-arabinopyranose glycosylated in positions 2, 3, or 4 with a β-d-xylopyranose or a β-d-glucopyranose residue, respectively, were synthesized in good to excellent yields. The saponins were then prepared in good yields through glycosylation with a suitably protected hederagenin derivative followed by total deprotection and treatment with diazomethane.