Proof of the local REM conjecture for number partitioning. II. Growing energy scales

We continue our analysis of the number partitioning problem with n weights chosen i.i.d. from some fixed probability distribution with density ρ. In Part I of this work, we established the so‐called local REM conjecture of Bauke, Franz and Mertens. Namely, we showed that, as n → ∞, the suitably rescaled energy spectrum above some fixed scale α tends to a Poisson process with density one, and the partitions corresponding to these energies become asymptotically uncorrelated. In this part, we analyze the number partitioning problem for energy scales α_n that grow with n, and show that the local REM conjecture holds as long as n^‐1/4α_n → 0, and fails if α_n grows like κn^1/4 with κ > 0. We also consider the SK‐spin glass model, and show that it has an analogous threshold: the local REM conjecture holds for energies of order o(n), and fails if the energies grow like κn with κ > 0. © 2008 Wiley Periodicals, Inc. Random Struct. Alg., 2009     

Spectroscopy: the study of DNA cleavage by newly synthesized polydentate macrocyclic ligand and its copper(II) complexes

A novel hexadentate nitrogen donor [N6] macrocyclic ligand, i.e. 2,6,12,16,21,22-hexaaza-3,5,13,15-tetramethyl-4,14-diethyl-tricyclo-[15.3.1.1(7-11)]docosane-1(21),2,5,7(22),8,10,12,15,17,19-decaene (L), has been synthesized. Copper(II) complexes with this ligand have been prepared and subjected to elemental analyses, molar conductance measurements, magnetic susceptibility measurements, mass, 1H NMR (ligand), IR, electronic, and EPR spectral studies. On the basis of molar conductance the complexes may be formulated as [Cu(L)X2] [X = Cl(-), Br(-), NO3(-) and CH3COO(-)] due to their nonelectrolytic nature in N,N'-dimethylformamide (DMF). All the complexes are of the high spin type and are six coordinated. On the basis of IR, electronic and EPR spectral studies tetragonal geometry has been assigned to the Cu(II) complexes. The interaction of these complexes with calf thymus DNA has been explored by using absorption, emission, viscosity measurements, electrochemical studies and DNA cleavage. All the experimental results suggest that the complexes bind to DNA and also promote the cleavage plasmid pBR 322, in the presence of H2O2 and ascorbic acid.     

IR-UV double resonance spectroscopic investigation of phenylacetylene-alcohol complexes. Alkyl group induced hydrogen bond switching

The electronic transitions of phenylacetylene complexes with water and trifluoroethanol are shifted to the blue, while the corresponding transitions for methanol and ethanol complexes are shifted to the red relative to the phenylacetylene monomer. Fluorescence dip infrared (FDIR) spectra in the O-H stretching region indicate that, in all the cases, phenylacetylene is acting as a hydrogen bond acceptor to the alcohols. The FDIR spectrum in the acetylenic C-H stretching region shows Fermi resonance bands for the bare phenylacetylene, which act as a sensitive tool to probe the intermolecular structures. The FDIR spectra reveal that water and trifluoroethanol interact with the pi electron density of the acetylene C-C triple bond, while methanol and ethanol interact with the pi electron density of the benzene ring. It can be inferred that the hydrogen bonding acceptor site on phenylacetylene switches from the acetylene pi to the benzene pi with lowering in the partial charge on the hydrogen atom of the OH group. The most significant finding is that the intermolecular structures of water and methanol complexes are notably distinct, which, to the best of our knowledge, this is first such observation in the case of complexes of substituted benzenes.     

Dual activation in asymmetric allylsilane addition to chiral N-acylhydrazones: method development, mechanistic studies, and elaboration of homoallylic amine adducts

[reaction: see text] Chiral N-acylhydrazones derived from commercially available 4-benzyl-2-oxazolidinone provide a rigid, conformationally restricted template to impart facial selectivity in additions to C=N bonds. In the presence of indium(III) trifluoromethanesulfonate [In(OTf)3], N-acylhydrazones undergo highly diastereoselective fluoride-initiated additions of allylsilanes (aza-Sakurai reaction). Mechanistic studies including control experiments and comparisons with allyltributylstannane, allylmagnesium bromide, and allylindium species implicate a dual activation mechanism involving addition of an allylfluorosilicate species to a chelate formed from In(OTf)3 and the chiral N-acylhydrazone. The N-N bonds of the adducts are readily cleaved in a two-step protocol to provide synthetically useful homoallylic N-trifluoroacetamides. Further elaboration of the latter compounds through Wacker oxidation and olefin metathesis provides diversely functionalized building blocks and expands the potential applications of this C-C bond construction approach to asymmetric amine synthesis.     

Electronic Characterization of Vis–NIR Absorbing Noninnocent Ruthenium Oxyquinolate–merocyanine Complexes and their Photoacoustic Emission in Aqueous Micellar Solution†

The electronic and photophysical properties for a series of ruthenium(II) polypyridyl dyes are presented where a π-accepting 5-(vinyl-cyanine)-8-oxyquinolate class of ligand is incorporated to yield an improved vis–NIR absorption. A combination of computational, UV–vis–NIR absorption, phosphorescence emission and cyclic voltammetry studies are used to probe the influence of these ligands on complex electronic and photophysical properties. To assess their potential as vis–NIR photoacoustic contrast agents, select complexes were formulated in a PBS buffer/Tween® 20 solvent system. The p-quinolin-1-ium, 1,3,3-trimethyl-3H-indol-1-ium and 1,1,3-trimethyl-1H-benzo[e]indol-3-ium acceptor groups each impart a strong 680 nm optical absorption and photoacoustic emission on par with the performance exhibited by both the methylene blue and cryptocyanine commercial dyes.     

Rhodium-Catalyzed C8-Alkenylation of Isoquinolones with Maleimides

An efficient Rh(III)-catalyzed C−H alkenylation of N-protected isoquinolone with maleimides is reported. The carbonyl group of isoquinolone acts as an inherent directing group. Various N-substituents in the maleimide, including alkyl, aryl, and even H and −OH, were well tolerated under the developed reaction condition. This protocol showed broad substrate scope, good selectivity, and excellent yields. Hammett plot is also drawn to check the effect of substituents on the reaction progress.     

Theoretical study of the substituent effects on the S-H bond dissociation energy and ionization energy of 3-pyridinethiol: Prediction of novel antioxidant

The S-H bond dissociation enthalpies [BDE(S-H)] of a set of 5-X- and 6-X-3-pyridinethiols (X = F, Cl, CH3, OCH3, NH2, N(CH3)2, CF3, CN, and NO2) have been computed using the density functional theory based (RO)B3LYP procedure with 6-311++G(2df,2p) basis set. The effects of substituents on the BDE(S-H), proton affinity of the pyridinethiol anion [PA(S-)] and ionization energy (IE) are analyzed and their correlations with Hammett's substituent constants are examined. Subsequently, a series of 6-substituted 3-pyridinethiols have been explored to find out their antioxidant potentials. Finally, a number of 3-pyridinethiol based compounds are theoretically proposed as novel antioxidants.     

Direct glycosylation: synthesis of alpha-indoline ribonucleosides

A selective synthesis of α-anomers of indoline nucleosides is described. Ribonucleosides of indoline, dimethylindoline and 5-bromoindoline are readily prepared in good yield by reacting indoline bases directly with the protected sugar, 2,3-O-(1-methylethylidene) 5-O-(triphenylmethyl)-D-ribofuranose in dry ethanol or methylene chloride in presence of molecular sieves at 40-60 °C.     

Gold nano-popcorn-based targeted diagnosis, nanotherapy treatment, and in situ monitoring of photothermal therapy response of prostate cancer cells using surface-enhanced Raman spectroscopy

Prostate cancer is the second leading cause of cancer-related death among the American male population, and the cost of treating prostate cancer patients is about $10 billion/year in the United States. Current treatments are mostly ineffective against advanced-stage prostate cancer and are often associated with severe side effects. Driven by these factors, we report a multifunctional, nanotechnology-driven, gold nano-popcorn-based surface-enhanced Raman scattering (SERS) assay for targeted sensing, nanotherapy treatment, and in situ monitoring of photothermal nanotherapy response during the therapy process. Our experimental data show that, in the presence of LNCaP human prostate cancer cells, multifunctional popcorn-shaped gold nanoparticles form several hot spots and provide a significant enhancement of the Raman signal intensity by several orders of magnitude (2.5 × 10(9)). As a result, it can recognize human prostate cancer cells at the 50-cells level. Our results indicate that the localized heating that occurs during near-infrared irradiation can cause irreparable cellular damage to the prostate cancer cells. Our in situ time-dependent results demonstrate for the first time that, by monitoring SERS intensity changes, one can monitor photothermal nanotherapy response during the therapy process. Possible mechanisms and operating principles of our SERS assay are discussed. Ultimately, this nanotechnology-driven assay could have enormous potential applications in rapid, on-site targeted sensing, nanotherapy treatment, and monitoring of the nanotherapy process, which are critical to providing effective treatment of cancer.     

Synthesis, spectral and biological studies of nitrogen–sulphur donor macrocyclic ligands and their transition metals complexes

Mn(II), Co(II), Ni(II) and Cu(II) complexes have been synthesized with 22 and 24 membered tetramide macrocyclic ligands viz; 1,9,12,20-tetraaza-2,8,13,19-tetraone-5,16-dithiacyclodocosane [L¹] and 1,9,13,21-tetraaza-2,8,14,20-tetraone-5,17-dithiacyclotetracosane [L²] and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic EPR spectral studies and electrochemical properties. The molar conductance of all the complexes in DMSO solution is corresponding to 1:2 electrolyte. Thus these complexes may be formulated as [M(L′)]Cl₂ [where M = Mn(II), Co(II), Ni(II) and Cu(II) L′ = L¹ and L²]. On the basis of spectral studies a distorted octahedral geometry has been assigned for all the complexes. The ligands and their complexes were also screened in vitro against two pathogenic fungi (F. moniliformae and R. solani) to assess their growth inhibiting potential.