Template Syntheses Involving the Carbon Acid Nitroethane. Synthesis and Characterization of Copper(II) Complexes of a 16-membered Tetraaza Macrocycle

New square-planar Cu(II) complexes of 3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane and 1,11-diamino-6-methyl-6-nitro-4,8-diazaundecane cations have been prepared from the one-pot template condensation of [Cu(pn)₂]²⁺ (pn=1,3-diaminopropane) in MeOH with CH₂O and EtNO₂ in the presence of a noncoordinating base. Reduction of the nitro group in the (3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane)copper(II) cation, may be achieved by Zn/acid reduction. The Cu(II) complex of the reduced form of the ligand, namely (3,11-diammonio-3,11-dimethyl-1,5,9,13-tetraazacyclohexadecane)copper(II), has also characterized. With the macrocyclic ligand, rac and meso isomers have been identified, the meso form being the major product. Elemental analyses, i.r. and u.v.–vis. spectroscopy, f.a.b. mass spectra conductometric, magnetic measurements and cyclic voltammetry have been used to characterize the complexes.     

New formulation and relaxation to solve a concave-cost network flow problem

In this paper we study a minimum cost, multicommodity network flow problem in which the total cost is piecewise linear, concave of the total flow along the arcs. Specifically, the problem can be defined as follows. Given a directed network, a set of pairs of communicating nodes and a set of available capacity ranges and their corresponding variable and fixed cost components for each arc, the problem is to select for each arc a range and identify a path for each commodity between its source and destination nodes so as to minimize the total costs. We also extend the problem to the case of piecewise nonlinear, concave cost function. New mathematical programming formulations of the problems are presented. Efficient solution procedures based on Lagrangean relaxations of the problems are developed. Extensive computational results across a variety of networks are reported. These results indicate that the solution procedures are effective for a wide range of traffic loads and different cost structures. They also show that this work represents an improvement over previous work made by other authors. This improvement is the result of the introduction of the new formulations of the problems and their relaxations.     

Second-harmonic generation from monolayer Langmuir–Blodgett films of various push–pull pyridine and terpyridine metal complexes

The new ligands (E)-4-[2-(4-(N-methyl-N-hexadecylaminophenyl)ethenyl]pyridine (L¹) and 4′-(C₆H₄-p-N(Me)(hexadecyl))-2,2′:6′,2″-terpyridine (L²) were prepared along with their complexes [cis-Ir(CO)₂ClL¹], [fac-Os(CO)₃Cl₂L¹], [ZnCl₂L²] and [IrCl₃L²]. Whereas these complexes show a large second-order nonlinear optical (NLO) response at the molecular level, similar to that of related organic alkylated salts as evidenced by the Electric Field Induced Second-Harmonic (EFISH) generation technique, their Langmuir–Blodgett (LB) film susceptibility is lower than that of the salts.     

Synthesis and activity measurement of some water-gas shift reaction catalysts

The effect of calcination temperature on the activity and some properties of low temperature water gas shift reaction catalysts has been investigated. The activities of catalysts have been determined using a fixed bed catalytic reactor. The following results may be deduced from the present study. 1. The catalysts' total surface area decreased with increasing calcination temperature, presumably due to the partial sintering of the catalysts particles. 2. The presence of an amorphous CuO phase within the structure of some catalysts may be related to the desirable conditions prevailing during synthesis of the latter. 3. Observation of a similar trend between the increase in copper crystallite particle size and enhancement of catalyst activities with increasing calcination temperature demonstrates the important contribution made by the copper crystallite phase to the overall activities of water gas shift reaction catalysts. This revised version was published online in June 2006 with corrections to the Cover Date.     

Highly chemoselective reductive amination-coupling by one-pot reaction of aldehydes, HMDS and NaBH4

An efficient and highly chemoselective synthesis of symmetrical secondary amines via reductive amination of aldehydes with inexpensive and commercially available HMDS and sodium borohydride in high to quantitative yields is reported.     

Intra-elemental photoelectron line intensities and their significance to quantitative analysis

Intraelemental relative photoelectron line intensities for 20 pure elements obtained under ultrahigh vacuum (5·10^?9 torr) and high resolution with cleaned surfaces are presented. Theoretical and experimental aspects of relative photoelectron line intensities as well as other characteristics of significance to quantitative analysis are discussed. Experimental data are related to theoretical results and compared with other recent work.     

Amperometric detection for liquid chromatographic separation of polynuclear hydrocarbons

Oxidative electrochemical detection is used for liquid chromatographic separation of polynuclear aromatic hydrocarbons (PAH's). The amperometric response is shown to be dependent on the working potential, ionic strength, flow rate, pH, temperature and pretreatment of the glassy carbon electrode surface. These experimental factors were optimized by choosing the maximum signal-to-noise ratio for anthracene and benz(a)-anthracene. The figures of merit (sensitivity, limit of detection and linear dynamic range) of six PAH's are reported and compared with ultraviolet absorption detection. Varying the applied potential gives the capability for selective detection.     

Origin of Fluorescence Lifetimes in Human Serum Albumin. Studies on Native and Denatured Protein

Human serum albumin consists of a single polypeptide of 585 amino acid residues with 1 Trp residue. In the present work, we measured fluorescence lifetimes of the protein in both native and denatured states. The results indicate that Trp emission occurs with three lifetimes in both states. Lifetimes values and contribution to the global emission decay differ between the two states. Data are interpreted as the results of an emission occurring from three substructures of the tryptophan formed in the excited state. Two of these substructures are already present for the tryptophan free in solution. The third lifetime is the result of the interaction between the tryptophan residue and surrounding microenvironment. The populations of these substructures characterized by the pre-exponential parameters of the fluorescence lifetimes are dependent on the fluorophore microenvironment and on the global protein structure.     

Tungstate sulfuric acid (TSA)/KMnO4 as a novel heterogeneous system for rapid deoximation

Neat chlorosulfonic acid reacts with anhydrous sodium tungstate to give tungstate sulfuric acid (TSA), a new dibasic inorganic solid acid in which two sulfuric acid molecules connect to a tungstate moiety via a covalent bond. A variety of oximes were oxidized to their parent carbonyl compounds under mild conditions with excellent yields in short times by a heterogeneous wet TSA/KMnO4 in dichloromethane system.     

Clustering Categorical Data via Ensembling Dissimilarity Matrices

We present a technique for clustering categorical data by generating many dissimilarity matrices and combining them. We begin by demonstrating our technique on low-dimensional categorical data and comparing it to several other techniques that have been proposed. We show through simulations and examples that our method is both more accurate and more stable. Then we give conditions under which our method should yield good results in general. Our method extends to high-dimensional categorical data of equal lengths by ensembling over many choices of explanatory variables. In this context, we compare our method with two other methods. Finally, we extend our method to high-dimensional categorical data vectors of unequal length by using alignment techniques to equalize the lengths. We give an example to show that our method continues to provide useful results, in particular, providing a comparison with phylogenetic trees. Supplementary material for this article is available online.