Using CLEM to investigate the distribution of nano-sized antimicrobial agents within an EVOH matrix

Efficient characterization of the distribution of antimicrobial agents within a polymer matrix is of vital importance. Two antimicrobial agents, chitin nanowhiskers (ChNWs) and chitosan-based silver nanoparticles (CTSAgNPs), were produced and incorporated separately as well as combined into a poly(ethylene-co-vinyl alcohol) (EVOH) matrix by way of electrospinning. Correlative light and electron microscopy (CLEM) and energy dispersive X-ray mapping provided a holistic approach to visualize the distribution of the combinations of AgNPs and ChNWs within EVOH fibers. CLEM analysis revealed the tendency of the ChNWs to align themselves on the surface of the fibers, while the silver nanoparticles were localized inside the polymer matrix.     

The order of hypotraceable oriented graphs

A digraph of order n is hypotraceable if it is nontraceable but all its induced subdigraphs of order n−1 are traceable. Grötschel et al. (1980) [M. Grötschel, C. Thomassen, Y. Wakabayashi, Hypotraceable digraphs, J. Graph Theory 4 (1980) 377–381] constructed an infinite family of hypotraceable oriented graphs, the smallest of which has order 13. We show that there exist hypotraceable oriented graphs of order n for every n≥8 except possibly for n=9,11 and that is the only one of order less than 8.Furthermore, we determine all the hypotraceable oriented graphs of order 8 and explain the relevance of these results to the problem of determining, for given k≥2, the maximum order of nontraceable oriented digraphs each of whose induced subdigraphs of order k is traceable.     

Tuning the reactivity in classic low-spin d6 rhenium(I) tricarbonyl radiopharmaceutical synthon by selective bidentate ligand variation (L,L'-Bid; L,L'= N,N', N,O, and O,O' donor atom sets) in fac-[Re(CO)3(L,L'-Bid)(MeOH)]n complexes

A range of fac-[Re(CO)(3)(L,L'-Bid)(H(2)O)](n) (L,L'-Bid = neutral or monoanionic bidentate ligands with varied L,L' donor atoms, N,N', N,O, or O,O': 1,10-phenanthroline, 2,2'-bipydine, 2-picolinate, 2-quinolinate, 2,4-dipicolinate, 2,4-diquinolinate, tribromotropolonate, and hydroxyflavonate; n = 0, +1) has been synthesized and the aqua/methanol substitution has been investigated. The complexes were characterized by UV-vis, IR and NMR spectroscopy and X-ray crystallographic studies of the compounds fac-[Re(CO)(3)(Phen)(H(2)O)]NO(3)·0.5Phen, fac-[Re(CO)(3)(2,4-dQuinH)(H(2)O)]·H(2)O, fac-[Re(CO)(3)(2,4-dQuinH)Py]Py, and fac-[Re(CO)(3)(Flav)(CH(3)OH)]·CH(3)OH are reported. A four order-of-magnitude of activation for the methanol substitution is induced as manifested by the second order rate constants with (N,N'-Bid) < (N,O-Bid) < (O,O'-Bid). Forward and reverse rate and stability constants from slow and stopped-flow UV/vis measurements (k(1), M(-1) s(-1); k(-1), s(-1); K(1), M(-1)) for bromide anions as entering nucleophile are as follows: fac-[Re(CO)(3)(Phen)(MeOH)](+) (50 ± 3) × 10(-3), (5.9 ± 0.3) × 10(-4), 84 ± 7; fac-[Re(CO)(3)(2,4-dPicoH)(MeOH)] (15.7 ± 0.2) × 10(-3), (6.3 ± 0.8) × 10(-4), 25 ± 3; fac-[Re(CO)(3)(TropBr(3))(MeOH)] (7.06 ± 0.04) × 10(-2), (4 ± 1) × 10(-3), 18 ± 4; fac-[Re(CO)(3)(Flav)(MeOH)] 7.2 ± 0.3, 3.17 ± 0.09, 2.5 ± 2. Activation parameters (ΔH(k1)(++), kJmol(-1); ΔS(k1)(), J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Re(CO)(3)(Phen)(MeOH)](+) iodide 70 ± 1, -35 ± 3; fac-[Re(CO)(3)(2,4-dPico)(MeOH)] bromide 80.8 ± 6, -8 ± 2; fac-[Re(CO)(3)(Flav)(MeOH)] bromide 52 ± 5, -52 ± 15. A dissociative interchange mechanism is proposed.     

Structures of rhenium(I) complexes with 3‐hydroxyflavone and benzhydroxamic acid as O,O′‐bidentate ligands and confirmation of π‐stacking by solid‐state NMR spectroscopy

The synthesis and crystal structures of two new rhenium(I) complexes obtained utilizing benzhydroxamic acid (BHAH) and 3‐hydroxyflavone (2‐phenylchromen‐4‐one, FlavH) as bidentate ligands, namely tetraethylammonium fac‐(benzhydroxamato‐κ²O,O′)bromidotricarbonylrhenate(I), (C₈H₂₀N)[ReBr(C₇H₆NO₂)(CO)₃], 1 , and fac‐aquatricarbonyl(4‐oxo‐2‐phenylchromen‐3‐olato‐κ²O,O′)rhenium(I)–3‐hydroxyflavone (1/1), [Re(C₁₅H₉O₃)(CO)₃(H₂O)]·C₁₅H₁₀O₃, 3 , are reported. Furthermore, the crystal structure of free 3‐hydroxyflavone, C₁₅H₁₀O₃, 4 , was redetermined at 100 K in order to compare the packing trends and solid‐state NMR spectroscopy with that of the solvate flavone molecule in 3 . The compounds were characterized in solution by ¹H and ¹³C NMR spectroscopy, and in the solid state by ¹³C NMR spectroscopy using the cross‐polarization magic angle spinning (CP/MAS) technique. Compounds 1 and 3 both crystallize in the triclinic space group P with one molecule in the asymmetric unit, while 4 crystallizes in the orthorhombic space group P2₁2₁2₁. Molecules of 1 and 3 generate one‐dimensional chains formed through intermolecular interactions. A comparison of the coordinated 3‐hydroxyflavone ligand with the uncoordinated solvate molecule and free molecule 4 shows that the last two are virtually completely planar due to hydrogen‐bonding interactions, as opposed to the former, which is able to rotate more freely. The differences between the solid‐ and solution‐state ¹³C NMR spectra of 3 and 4 are ascribed to inter‐ and intramolecular interactions. The study also investigated the potential labelling of both bidentate ligands with the corresponding fac‐^99mTc‐tricarbonyl synthon. All attempts were unsuccessful and reasons for this are provided.     

An Infinite Family of Planar Hypohamiltonian Oriented Graphs

Carsten Thomassen asked in 1976 whether there exists a planar hypohamiltonian oriented graph. We answer his question by presenting an infinite family of planar hypohamiltonian oriented graphs, the smallest of which has order 9. A computer search showed that 9 is the smallest possible order of a hypohamiltonian oriented graph.     

Infinite families of 2-hypohamiltonian/2-hypotraceable oriented graphs

A digraph D of order n is r-hypohamiltonian (respectively r-hypotraceable) for some positive integer r < n ? 1 if D is nonhamiltonian (nontraceable) and the deletion of any r of its vertices leaves a hamiltonian (traceable) digraph. A 1-hypohamiltonian (1-traceable) digraph is simply called hypohamiltonian (hypotraceable). Although hypohamiltonian and hypotraceable digraphs are well-known and well-studied concepts, we have found no mention of r-hypohamiltonian or r-hypotraceable digraphs in the literature for any r > 1. In this paper we present infinitely many 2-hypohamiltonian oriented graphs and use these to construct infinitely many 2-hypotraceable oriented graphs. We also discuss an interesting connection between the existence of r-hypotraceable oriented graphs and the Path Partition Conjecture for oriented graphs.     

Proper connection and size of graphs

An edge-coloured graph $G$ is called properly connected if any two vertices are connected by a path whose edges are properly coloured. The proper connection number of a connected graph $G,$ denoted by $\mathrm{pc}\left(G\right)$, is the smallest number of colours that are needed in order to make $G$ properly connected. Our main result is the following: Let $G$ be a connected graph of order $n$ and $k\ge 2$. If $\left|E\left(G\right)\right|\ge \left(\genfrac{}{}{0ex}{}{n?k?1}{2}\right)+k+2$, then $\mathrm{pc}\left(G\right)\le k$ except when $k=2$ and $G\in \{G_1,G_2\},$ where $G_1=K_1\vee (2K_1+K_2)$ and $G_2=K_1\vee (K_1+2K_2).$