Independence and graph homomorphisms graph homomorphisms

A graph with n vertices that contains no triangle and no 5-cycle and minimum degree exceeding n/4 contains an independent set with at least (3n)/7 vertices. This is best possible. The proof proceeds by producing a homomorphism to the 7-cycle and invoking the No Homomorphism Lemma. For k ≥ 4, a graph with n vertices, odd girth 2k+1, and minimum degree exceeding n/(k+1) contains an independent set with at least kn/(2k+1) vertices; however, we suspect this is not best possible. © 1993 John Wiley & Sons, Inc.     

New method for the differentiation of the isomers of aminophenol

Summary Pyridine-2,6-dialdehyde is used as a reagent in a very simple and fast method for differentiating between theo- andp-isomers of aminophenol.

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Zusammenfassung Pyridin-2,6-aldehyd wurde für die einfache und schnelle Unterscheidung zwischen den o- und p-Isomeren des Aminophenols verwendet.

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Résumé On décrit une méthode simple et rapide dans laquelle Pyridine 2–6 aldehyde est employé pour distinguer entre les isomères de l'aminophénol.

     

Site-isolation effects in a dendritic nickel catalyst for the oligomerization of ethylene

Dendrimers, specifically suited to construct site-isolated groups due to their well-defined hyperbranched structure, have been used as a ligand design element for the construction of nickel catalysts for ethylene oligomerization. The dendritic P,O ligand indeed suppresses the formation of inactive bis(P,O)Ni complexes in toluene, as is evident from NMR studies, and, as a consequence, outperforms the parent ligand in catalysis in this solvent. The dendritic effect observed in methanol is more subtle because both the dendritic ligand 1 and the parent 2 form bis(P,O)nickel complexes in solution according to NMR spectroscopy. Unlike the parent complex 8, the dendritic bis(P,O)Ni complex 7 derived from dendrimer ligand 1 is able to dissociate to a mono-ligated species under catalytic conditions, that is, 40 bar ethylene and 80 degrees C, which can enter the catalytic cycle. Indeed, dendritic ligand 1 gives much more active nickel catalysts for the oligomerization in methanol than does 2.     

Synthesis of a diverse library of mechanism-based cysteine protease inhibitors

We report improvements of our method for the solid-phase synthesis of mechanism-based mercaptomethyl ketone inhibitors of cysteine proteases (Lee, A.; Huang, L.; Ellman, J. A. J. Am. Chem. Soc. 1999, 121, 9907-9914). Specifically, Fmoc-protected chloromethyl ketones were used, rather than the Alloc-protected counterparts. In addition, we further demonstrated that diverse polar functionality can be incorporated at the R1', R1, and R2 sites, in contrast to our previous efforts, where primarily hydrophobic groups were incorporated at these positions. On the basis of these results, a 2016-membered library of potential mercaptomethyl ketone inhibitors was prepared that incorporated diverse functionality. The library was screened against cathepsin B, which is implicated in cancer, resulting in the identification of single-digit nanomolar inhibitors. Because of the diverse functionality incorporated in this library, it should be a rich source of potent inhibitors against many other cysteine proteases.     

Generation of new landomycins by combinatorial biosynthetic manipulation of the LndGT4 gene of the landomycin E cluster in S. globisporus

A 3 kb DNA fragment from the Streptomyces globisporus 1912 landomycin E (LaE) biosynthetic gene cluster (lnd) was completely sequenced. Three open reading frames were identified, lndGT4, lndZ4, and lndZ5, whose probable translation products resemble a glycosyltransferase, a reductase, and a hydroxylase, respectively. Studies of generated mutants from disruption and complementation experiments involving the lndGT4 gene allowed us to determine that LndGT4 controls the terminal L-rhodinose sugar attachment during LaE biosynthesis and that LndZ4/LndZ5 are responsible for the unique C11-hydroxylation of the landomycins. Generation of the novel landomycins F, G, and H in the course of these studies provided evidence for the flexibility of lnd glycosyltransferases toward their acceptor substrates and a basis for initial structure-activity relationships within the landomycin family of antibiotics.     

Structural, spectral and thermal studies of N-2-(4-picolyl)- and N-2-(6-picolyl)-N′-(2-chlorophenyl)thioureas and N-2-(6-picolyl)-N′-(2-bromophenyl)thiourea

N-2-(4-picolyl)-N′-2-chlorophenylthiourea, 4PicTu2Cl, monoclinic, P2₁/c, a=10.068(5), b=11.715(2), β=96.88(4)°, and Z=4; N-2-(6-picolyl)-N′-2-chlorophenylthiourea, 6PicTu2Cl, triclinic, P-1, a=7.4250(8), b=7.5690(16), c=12.664(3) Å, =105.706(17), β=103.181(13), γ=90.063(13)°, V=665.6(2) ų and Z=2 and N-2-(6-picolyl)-N′-2-bromophenylthiourea, 6PicTu2Br, triclinic, P-1, a=7.512(4), b=7.535(6), c=12.575(4) Å, a=103.14(3), β=105.67(3), γ=90.28(4)°, V=665.7(2) ų and Z=2. The intramolecular hydrogen bonding between N′H and the pyridine nitrogen and intermolecular hydrogen bonding involving the thione sulfur and the NH hydrogen, as well as the planarity of the molecules, are affected by the position of the methyl substituent on the pyridine ring. The enthalpies of fusion and melting points of these thioureas are also affected. ¹H NMR studies in CDCl₃ show the NH′ hydrogen resonance considerably downfield from other resonances in their spectra.     

Effect of ammonia,ammonia-water,and sulfuric acid on the HO2 + HO2 → H2O2 + 3O2 reaction in troposphere: Competition between stepwise and one-step mechanisms

A detailed theoretical study on the reaction mechanisms for the formations of H₂O₂ + ³O₂ from the self-reaction of HO₂ radicals under the effect of NH₃, H₃N···H₂O, and H₂SO₄ catalysts was performed using the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ method. The rate constant was computed using canonical variational transition state theory (CVT) with small curvature tunneling (SCT). Our results indicate that NH₃-, H₃N···H₂O-, and H₂SO₄-catalyzed reactions could proceed through both one-step and stepwise routes. Calculated rate constants show that the catalyzed routes in the presence of the three catalysts all prefer stepwise pathways. Compared to the catalytic efficiency of H₂O, the efficiencies of NH₃, H₃N···H₂O, and H₂SO₄ are much lower due to their smaller relative concentrations. The present results have provided a definitive example of how basic and acidic catalysts influence the atmospheric reaction of HO₂ + HO₂ → H₂O₂ + ³O₂. These results further encourage one to consider the effects of basic and acidic catalysts on the related atmospheric reactions. Thus, the present investigation should have broad implications in the gas-phase reactions of the atmosphere.     

Electromagnetic acceleration of the Belousov-Zhabotinski reaction

Acceleration of the Belousov-Zhabotinski (BZ) reaction, in stirred homogeneous solutions, by low frequency electromagnetic (EM) fields has provided new insights into EM interaction mechanisms. The acceleration varies inversely with the basal reaction rate, indicating that the applied magnetic field and the intrinsic chemical driving forces affect the same electron transfer reaction. The amplitude and frequency dependence of the EM field interactions are also consistent with interaction during electron transfer. A mechanism based on interaction with moving electrons offers a way of explaining the ability of EM fields to stimulate gene expression, in particular the stress response, since electrons have been shown to move in DNA.     

Hopping type of conduction in (Na0.5Bi0.5)ZrO3 ceramic

Polycrystalline sample with (Na_0.5Bi_0.5)ZrO₃ (NBZ) stoichiometry was prepared using a high-temperature solid-state reaction technique. X-ray diffraction (XRD) analyses indicate the formation of a single-phase perovskite-type orthorhombic structure. AC impedance plot is used as tool to analyse the electrical behaviour of the sample as a function of temperature at different frequency. The AC impedance studies revealed the presence of grain boundary effect and evidence of a negative temperature coefficient of resistance (NTCR) character. Pseudo Cole-Cole and complex electric modulus analyses indicated non-Debye-type dielectric relaxation. The AC conductivity obeys the universal power law. The pair approximation type correlated barrier hopping (CBH) model explains the universal behaviour of the s exponent. The apparent activation energy to the conduction process and minimum hopping distance are discussed.     

An Integrative Pathway-based Clinical-genomic Model for Cancer Survival Prediction

Prediction models that use gene expression levels are now being proposed for personalized treatment of cancer, but building accurate models that are easy to interpret remains a challenge. In this paper, we describe an integrative clinical-genomic approach that combines both genomic pathway and clinical information. First, we summarize information from genes in each pathway using Supervised Principal Components (SPCA) to obtain pathway-based genomic predictors. Next, we build a prediction model based on clinical variables and pathway-based genomic predictors using Random Survival Forests (RSF). Our rationale for this two-stage procedure is that the underlying disease process may be influenced by environmental exposure (measured by clinical variables) and perturbations in different pathways (measured by pathway-based genomic variables), as well as their interactions. Using two cancer microarray datasets, we show that the pathway-based clinical-genomic model outperforms gene-based clinical-genomic models, with improved prediction accuracy and interpretability.