Synthesis and Characterization of Four-Arm Star Poly(ϵ-caprolactone)-Block-Poly(cyclic-carbonate methacrylate) Copolymers by Combining Ring-Opening Polymerization With Atom Transfer Radical Polymerization

Well-defined four-arm star poly(?-caprolactone)-block-poly(cyclic carbonate methacrylate) (PCL-b-PCCMA) copolymers were synthesized by combining ring-opening polymerization (ROP) with atom transfer radical polymerization (ATRP). First, a four-arm poly(?-caprolactone) (PCL) macroinitiator [(PCL-Br)₄] was prepared by the ROP of ?-CL catalyzed by stannous octoate at 110°C in the presence of pentaerythritol as the tetrafunctional initiator followed by esterification with 2-bromoisobutyryl bromide. The sequential ATRP of CCMA monomer was carried out by using the (PCL-Br)₄ tetrafunctional macroinitiator (MI) and in the presence of CuBr/2, 2′-bipyridyl system in DMF at 80°C with [(MI)]:[CuBr]:[bipyridyl] = 1:1:3 to yield block polymers with controlled molecular weights (M_n (NMR) = 10700 to 27300 g/mol) by varying block lengths and with moderately narrow polydispersities (M_w/M_n = 1.2–1.4). Block copolymers with different PCL: PCCMA copolymer composition such as 50:50, 70:30 and 74:26 were prepared with good yields (48-74%). All these block copolymers were well characterized by NMR, FTIR and GPC and tested their thermal properties by DSC and TGA.     

Calotropis procera extract induces apoptosis and cell cycle arrest at G2/M phase in human skin melanoma (SK-MEL-2) cells

Calotropis procera (family: Asclepiadaceae) contains cardiac glycosides which are cytotoxic to cancer cells. The extracts of C. procera have been reported to be cytotoxic to many cancer cell lines and this is the first report against the human skin melanoma cells (SK-MEL-2). The SK-MEL-2 cells treated with C. procera methanolic extract (CPME) were analysed for growth inhibition and apoptosis. The exposure of phosphatidylserine in apoptotic SK-MEL-2 was analysed by using the Annexin-V FITC flow cytometry method. In CPME-treated SK-MEL-2 cells, 19.6% of apoptotic and 58.3% dead cells were observed. The 15.97% and 15.85% of early apoptotic cells were found at 20 μg/mL of the ouabain and paclitaxel, respectively. Active caspases, nuclear degradation confirmed apoptotic SK-MEL-2 cells in time- and dose-dependent manner. The cell cycle analysis shows that CPME treated cells halt at G2/M phase. Significant cytotoxic activity of CPME against SK-MEL-2 may be attributed to its high cardenolide content.     

The struction of a graph: Application toCN-free graphs

We consider the class of graphs characterized by the forbidden subgraphsC andN:C is the claw (unique graph with degree sequence (3, 1, 1, 1)) andN the net (unique graph with degree sequence (3, 3, 3, 1, 1, 1)). For this class of graphs (calledCN-free) an algorithm is described for determining the stability numberα(G). It is based on a construction associating with anyCN-free graphG anotherCN-free graphG′ such thatα(G′)=α(G)−1. Such a construction reducing the stability number is called a struction. This work was completed while this author was visiting the Dept. of Combinatories and Optimization at the University of Waterloo, Ontario.     

Polar cographs

Polar graphs are a natural extension of some classes of graphs like bipartite graphs, split graphs and complements of bipartite graphs. A graph is (s,k)-polar if there exists a partition A,B of its vertex set such that A induces a complete s-partite graph (i.e., a collection of at most s disjoint stable sets with complete links between all sets) and B a disjoint union of at most k cliques (i.e., the complement of a complete k-partite graph).Recognizing a polar graph is known to be NP-complete. These graphs have not been extensively studied and no good characterization is known. Here we consider the class of polar graphs which are also cographs (graphs without induced path on four vertices). We provide a characterization in terms of forbidden subgraphs. Besides, we give an algorithm in time O(n) for finding a largest induced polar subgraph in cographs; this also serves as a polar cograph recognition algorithm. We examine also the monopolar cographs which are the (s,k)-polar cographs where min(s,k)?1. A characterization of these graphs by forbidden subgraphs is given. Some open questions related to polarity are discussed.     

Four classes of perfectly orderable graphs

A graph is called “perfectly orderable” if its vertices can be ordered in such a way that, for each induced subgraph F, a certain “greedy” coloring heuristic delivers an optimal coloring of F. No polynomial-time algorithm to recognize these graphs is known. We present four classes of perfectly orderable graphs: Welsh–Powell perfect graphs, Matula perfect graphs, graphs of Dilworth number at most three, and unions of two threshold graphs. Graphs in each of the first three classes are recognizable in a polynomial time. In every graph that belongs to one of the first two classes, we can find a largest clique and an optimal coloring in a linear time.     

Synthesis and bioactivities of some new 1H-pyrazole derivatives containing an aryl sulfonate moiety

A new series of 1H-pyrazole derivatives 5a-j bearing an aryl sulfonate moiety have been synthesized by a one-pot cyclo-condensation reaction of 2-(3-(dimethylamino)acryloyl)phenyl-4-methyl benzene sulfonates 4a-e and hydrazine hydrate or phenyl hydrazine in ethanol under reflux conditions.Some of the newly synthesized compounds were screened for their anti-inflammatory activity.All synthesized compounds were screened against Gram positive and Gram negative bacterial and fungal strains.The compound 5b was found to be a potent anti-inflammatory agent while the majority of the compounds were found to be active against microbial strains.     

Gold-catalyzed formal [3 + 3] and [4 + 2] cycloaddition reactions of nitrosobenzenes with alkenylgold carbenoids

We report two new formal cycloaddition reactions between nitrosobenzenes and alkenylgold carbenoids. We obtained quinoline oxides 3 in satisfactory yields from the gold-catalyzed [3 + 3]-cycloadditions between nitrosobenzenes and alkenyldiazo esters 1. For propargyl esters 5, its resulting gold carbenes react with nitrosobenzene to give alkenylimine 8, followed by a [4 + 2]-cycloaddition with nitrosobenzene.     

ZnII‐ and AuI‐Catalyzed Regioselective Hydrative Oxidations of 3‐En‐1‐ynes with Selectfluor: Realization of 1,4‐Dioxo and 1,4‐Oxohydroxy Functionalizations

Catalytic 1,4‐dioxo functionalizations of 3‐en‐1‐ynes to (Z)‐ and (E)‐2‐en‐1,4‐dicarbonyl compounds are described. This regioselective difunctionalization was achieved in one‐pot operation through initial alkyne hydration followed by in situ Selectfluor oxidation. The presence of pyridine alters the reaction chemoselectivity to give 4‐hydroxy‐2‐en‐1‐carbonyl products instead. A cooperative action of pyridine and Zn^II assists the hydrolysis of key oxonium intermediate.     

Equistable graphs

An equistable graph is a graph for which the incidence vectors of the maximal stable sets are the 0–1 solutions of a linear equation. A necessary condition and a sufficient condition for equistability are given. They are used to characterize the equistability of various classes of perfect graphs, outerplanar graphs, and pseudothreshold graphs. Some classes of equistable graphs are shown to be closed under graph substitution.     

On a conjecture of wang and williams

Wang and Williams defined a threshold assignment for a graph G as an assignment of a non-negative weight to each vertex and edge of G, and a threshold t, such that a set S of vertices is stable if and only if the total weight of the subgraph induced by S does not exceed t - 1. This is always possible with zero vertex-weights, unit edge-weights, and t = 1. By definition, a threshold graph is a graph having a threshold assignment with zero edge-weights. The threshold weight of G is the minimum total edgeweight of a threshold assignment of G. A graph G = (V,E) is called heavy if its threshold weight is |E|. A clique C of G is called big if |E(C)| > |E(G - C)|. Wang and Williams showed that graphs with a big clique are not heavy, and conjectured the converse. They verified the conjecture for triangle-free graphs. We disprove the conjecture in general, but prove it for perfect graphs.