Solution of a Conjecture of Volkmann on the Number of Vertices in Longest Paths and Cycles of Strong Semicomplete Multipartite Digraphs

 A digraph obtained by replacing each edge of a complete multipartite graph by an arc or a pair of mutually opposite arcs with the same end vertices is called a semicomplete multipartite digraph. L. Volkmann conjectured that l≤2c−1, where l (c, respectively) is the number of vertices in a longest path (longest cycle) of a strong semicomplete multipartite digraph. The bound on l is sharp. We settle this conjecture in affirmative. Received: October 26, 1998?Final version received: August 16, 1999     

Evaluation of Isoprene Chain Extension from PEO Macromolecular Chain Transfer Agents for the Preparation of Dual, Invertible Block Copolymer Nanoassemblies

Two RAFT-capable PEO macro-CTAs, 2 and 5 kDa, were prepared and used for the polymerization of isoprene which yielded well-defined block copolymers of varied lengths and compositions. GPC analysis of the PEO macro-CTAs and block copolymers showed remaining unreacted PEO macro-CTA. Mathematical deconvolution of the GPC chromatograms allowed for the estimation of the blocking efficiency, about 50% for the 5 kDa PEO macro-CTA and 64% for the 2 kDa CTA. Self assembly of the block copolymers in both water and decane was investigated and the resulting regular and inverse assemblies, respectively, were analyzed with DLS, AFM, and TEM to ascertain their dimensions and properties. Assembly of PEO-b-PIp block copolymers in aqueous solution resulted in well-defined micelles of varying sizes while the assembly in hydrophobic, organic solvent resulted in the formation of different morphologies including large aggregates and well-defined cylindrical and spherical structures.     

Small degree out‐branchings

Using a suitable orientation, we give a short proof of a strengthening of a result of Czumaj and Strothmann 4 : Every 2‐edge‐connected graph G contains a spanning tree T with the property that for every vertex v. As an analogue of this result in the directed case, we prove that every 2‐arc‐strong digraph D has an out‐branching B such that . A corollary of this is that every k‐arc‐strong digraph D has an out‐branching B such that , where . We conjecture that in this case would be the right (and best possible) answer. If true, this would again imply a strengthening of a result from 4 concerning spanning trees with small degrees in k‐connected graphs when k ≥ 2. We prove that for acyclic digraphs the existence of an out‐branching satisfying prescribed bounds on the out‐degrees of each vertex can be checked in polynomial time. A corollary of this is that the existence of arc‐disjoint branchings , , where the first is an out‐branching rooted at s and the second an in‐branching rooted at t, can be checked in polynomial time for the class of acyclic digraphs © 2003 Wiley Periodicals, Inc. J Graph Theory 42: 297–307, 2003     

Structural studies of N-2-(6-picolyl)-N′-tolylthioureas

Reaction of 2-amino-6-picoline with 2-, 3-, and 4-tolyl isothiocyanates produces the three N-2-(6-picolyl)-N-tolylthioureas, 6PicTu2T, 6PicTu3T, and 6PicTu4T. 6PicTu2T is mono-clinic, space group P2₁/n with a = 8.1700(3) Å, b = 25.5840(6) Å, c = 12.6840(5) Å, = 98.8750(16)°, and V = 2619.5(2) ų with Z = 8, for d _calc = 1.305 g/cm³. 6PicTu3T is monoclinic, space group C2/c with a = 23.879(3) Å, b = 6.744(3) Å, c = 17.116(10) Å, = 99.26(4)°, and V = 2720(3) ų with Z = 8, for d _calc = 1.257 g/cm³. 6PicTu4T is triclinic, space group P-1 with a = 8.829(6) Å, b = 8.8950(15) Å, c = 10.495(3) Å, = 68.63(3)°, = 72.19(4)°, = 63.06(4)°, and V = 681.2(5) ų with Z = 2, for d _calc = 1.255 g/cm³. Intermolecular hydrogen bonding involving the thione sulfur and the NH hydrogen and the planarity of the thiourea are affected by the position of substitution on the aryl ring. ¹H NMR studies in CDCl₃ show the NH hydrogen resonance considerably downfield from other signals in the spectrum of each thiourea. The enthalpies of fusion of the present thioureas reflect the extent of intermolecular hydrogen bonding and are compared to other heterocyclic thioureas.     

Jet-cooled laser spectroscopy of the cyclohexoxy radical

The laser-induced fluorescence and laser-excited dispersed fluorescence spectra of the cyclohexoxy radical has been observed under two sets of free-jet-cooling conditions, characterized by rotational temperatures of approximately 1 and 100 K. Although five conformers of cyclohexoxy are possible, it appears that all presently observed spectral bands can be accounted for by a single one. All cold spectral bands are assigned to the B-X electronic transition of the cyclohexoxy radical. Transitions to both a' and a" B state vibrational levels are observed and allowed due to a substantial pseudo-Jahn-Teller effect in the X state. Hot bands are also observed, which we attributed to transitions to the B state from the low-lying A electronic state. Analysis of the spectra yields vibrational frequencies for the X, A, and B states as well as the energy separations of their vibrationless levels.     

Rapid uptake of oxidized ascorbate induces loss of cellular glutathione and oxidative stress in liver slices

The observation that ascorbate known to retain pro-oxidant properties induces cell death in a number of immortal cell lines, led us to examine its mechanism and whether it is involved in oxidative stress injury in such asocorbate-enriched tissue cells as hepatocytes. In rat liver homogenates, higher concentrations (1 and 3 mM) of ascorbate suppressed lipid peroxide productions but lower concentrations (0.1 and 0.3 mM) did not. In contrast to the homogenate, ascorbate increased lipid peroxide production in liver slices in a concentration dependant manner. Iso-ascorbate, the epimer of ascorbate did not cause an increase the oxidative stress in liver slices. This differential effect between homogenates and liver slices implies that cellular integrity is required for ascorbate to induce oxidative stress. Wortmannin, an inhibitor of the GLUT (glucose transporter) thought to transport dehydroascorbate into cells, inhibited [(14)C]-ascorbate uptake and suppressed oxidative stress in liver slices. Wortmannin suppressed that [(14)C]-ascorbate uptake by GLUT following oxidation to [(14)C]dehydroascorbate. Taken together, these observations support our hypothesis that ascorbate is oxidized to dehydroascorbate by molecular oxygen in solution (i.e., plasma and culture medium) which is then carried into hepatocytes (via a GLUT) where it is reduced back to ascorbate causing oxidative stress.     

ISOLATION AND PARTIAL CHARACTERIZATION OF THE PHOTOCHEMICAL REACTION CENTER OF CHROMATIUM VINOSUM (STRAIN D)

Abstract— –A preparation of the photochemical reaction center of Chromatiwn has been obtained by chromatography of lauryldimethylamineoxide-solubilized chromatophores on hydroxylapatite and Sepharose columns. The procedure has yielded a reaction center preparation from both carotenoid-containing and carotenoid-deficient Chromatium cells. Preliminary analysis of the isolated component indicates that the photochemical reaction center of the Thiorhodaceae is homologous to that of the Athiorhodaceae. In particular, the near infrared absorption spectrum of the Chromatium reaction center preparation shows the same triple-peaked spectrum observed for reaction center preparations from the Athiorhodaceae. The Chromatium preparation undergoes a rapid light-induced oxidation and dark reduction of the reaction center. The ratio of the reaction center to the two membrane-bound cytochromes (cytochrome c₅₅₂ and c₅₅₅) is greatly increased over the ratio observed in chromatophores or in other previously isolated, reaction center-enriched subchromatophore fractions of this organism.     

Metal scrambling in the trinuclear (Pt(2)Se(2)M)(M = Pt, Pd, Au) system using an electrospray mass spectrometry (ESMS) directed synthetic methodology; isolation and crystallographic characterization of (Pt(2)(mu(3)-Se)(2)(PPh(3))(4)[Pt(cod)])(PF(6))(2) and (Pt(mu(3)-Se)(2)(PPh(3))(2)[Pt(cod)](2))(PF(6))(2) (cod = cyclo-octa-1,5-diene)

Pt(2)(mu-Se)(2)(PPh(3))(4) reacts with PtCl(2)(cod) to give (Pt(2)(mu(3)-Se)(2)(PPh(3))(4)[Pt(cod)])(2+) and an unexpected cod-rich product that arises from metal scrambling, viz. (Pt(mu(3)-Se)(2)(PPh(3))(2)[Pt(cod)](2))(2+). The formation of these species was detected and followed by electrospray mass spectrometry (ESMS) and subsequently verified by batch synthesis and crystallographic characterization. Other metal-scrambled aggregate products were successfully detected.     

Metastable transitions in the mass spectra of ketals and ketones. Competition between loss of small and large radicals

An investigation of competing metastable transitions in the mass spectra of ethylene ketals R_SR_LC(OCH₂)₂ (where R_L is a larger n-alkyl group than R_S) has established that in most cases R_S is lost with a lower activation energy than R_L. This technique has also been applied to ketones R_SR_LC?O, to show again that R_S is usually lost with the lower activation energy (thus supporting earlier data based on relative daughter ion abundances at the threshold). In the classes of compounds so far investigated, although [M⁺ ? R_S] ions are formed with lower activation energies than [M⁺ ? R_L] ions, the ion yield of [M⁺ ? R_S] ions is anomalously low from ions of high internal energy. Factors which may influence the [M⁺ ? R_S]/[M⁺ ? R_L] ratio of daughter ion intensities are examined. It is suggested that at the threshold [M⁺ ? R_S] and [M⁺ ? R_L] ions may be formed with rearrangement, or from an electronic state that cannot be effectively populated from molecular ions of high internal energies.