Ca(2.5)Sr(0.5)GaMn2O8: diamagnetic Ga in control of the structural and electronic properties of a bilayered manganate

The temperature dependence of the crystal structure and electronic properties of brownmillerite-like Ca(2.5)Sr(0.5)GaMn(2)O(8) has been studied by neutron powder diffraction and muSR spectroscopy. The results show that short-range 2D magnetic order begins to develop within the perovskite-like bilayers of MnO(6) octahedra approximately 50 K above the 3D Néel temperature of approximately 150 K. The bilayers show a structural response to the onset of magnetism throughout this temperature range whereas the GaO(4) layers that separate the bilayers only respond below the 3D ordering temperature. XANES spectroscopy shows that the sample contains Mn(3+) and Mn(4+) cations in a 1:1 ratio, and the behavior in the region of the Néel transition is interpreted as a local charge ordering. Electron diffraction and high-resolution electron microscopy have been used to show that the local microstructure is more complex than the average structure revealed by neutron diffraction, and that microdomains exist in which the GaO(4) tetrahedra show different orientations. It is argued that the bonding requirements of diamagnetic gallium control the electronic behavior within the perovskite-like bilayers.     

Molybdenum-phosphorus triple bond stabilization by ancillary alkoxide ligation: synthesis and structure of a terminal phosphide tris-1-methylcyclohexanoxide complex

Using alcoholysis, we converted terminal phosphide PMo(N[i-Pr]Ar)3 into a new, monomeric terminal phosphide PMo(OR)3, where R = 1-methylcyclohexyl or 1-adamantyl. Dimerization of the PMo unit was observed upon alcoholysis with 2,6-dimethylphenol, and the dimer [PMo(N[i-Pr]Ar)(O-2,6-C6H3Me2)2]2 was isolated and characterized by X-ray crystallography.     

A New Generation of "Cholaphanes": Steroid-Derived Macrocyclic Hosts with Enhanced Solubility and Controlled Flexibility

The macrocyclic "cholaphanes" 3a-c were synthesized from the inexpensive steroid cholic acid. Like earlier relatives they feature substantial cavities with inward-directed hydroxyl groups, suitable for binding polar molecules such as carbohydrates in nonpolar media. New features are the externally directed alkyl chains, promoting solubility in organic solvents, and (in the case of 3b/c) reduced conformational freedom resulting from truncation of the steroidal side-chain. In particular, modeling shows that the smallest macrocycle 3c possesses very little flexibility, preferring an open conformation which is also revealed in the X-ray crystal structure of its pentahydrate. NMR studies indicated that all three cholaphanes form 1:1 complexes with octyl beta-D-glucoside in CDCl(3), with K(a) = 600-1560 M(-)(1). Cholaphanes 3b/c proved able to extract methyl beta-D-glucoside from aqueous solutions into CHCl(3). The transport of methyl beta-D-glucoside across a chloroform barrier was also demonstrated for 3c.     

Syntheses of seven-membered rings: ruthenium-catalyzed intramolecular [5+2] cycloadditions

The Ru-catalyzed intramolecular [5+2] cycloaddition of cyclopropylenynes is investigated with respect to the regio- and diastereoselectivity as well as the functional group compatibility of the reaction. Evidence for the mechanism as occurring through a ruthenacyclopentene intermediate is elucidated from 1) the study of the diastereoselectivity of the cycloaddition; 2) the effect of variation of substituents on the regioselectivity of cyclopropyl bond cleavage in 1,2-trans- and 1,2-cis-disubstituted cyclopropanes and 3) examples that clearly do not involve ruthenacyclohexene as intermediates as products still incorporate the cyclopropyl moiety. The scope and limitations of the Ru-catalyzed cycloaddition are discussed and compared with the Rh-catalyzed reaction. The potential power of this methodology towards natural product total synthesis is demonstrated by the formation of several polycyclic systems with the chosen reaction conditions and readily available cyclopropylenyne substrates.     

Structure of the first parallel DNA quadruplex-drug complex

The first crystal structure of a drug (daunomycin) bound to a parallel-stranded intermolecular telomeric G4 quadruplex (d(TGGGGT)4) has been determined to high resolution. A planar assemblage of three daunomycin molecules stacks onto the 5' end of the G4 column, with the daunosamine substituents occupying three of the four quadruplex grooves. The surface area of the terminal G-quartet in this parallel DNA quadruplex, presently occupied by three daunomycins, is sufficiently large that it could easily accommodate other potential telomerase inhibitors such as substituted porphyrins or telomestatin.     

N-Heterocyclic carbene–carbodiimide (NHC–CDI) betaine adducts: synthesis,characterization, properties,and applications

N-Heterocyclic carbenes (NHCs) are an important class of reactive organic molecules used as ligands, organocatalysts, and σ-donors in a variety of electroneutral ylide or betaine adducts with main-group compounds. An emerging class of betaine adducts made from the reaction of NHCs with carbodiimides (CDIs) form zwitterionic amidinate-like structures with tunable properties based on the highly modular NHC and CDI scaffolds. The adduct stability is controlled by the substituents on the CDI nitrogens, while the NHC substituents greatly affect the configuration of the adduct in the solid state. This Perspective is intended as a primer to these adducts, touching on their history, synthesis, characterization, and general properties. Despite the infancy of the field, NHC–CDI adducts have been applied as amidinate-type ligands for transition metals and nanoparticles, as junctions in zwitterionic polymers, and to stabilize distonic radical cations. These applications and potential future directions are discussed.

N-heterocyclic carbene-carbodiimide betaine adducts are zwitterionic amidinate-like structures with tunable properties that have applications as ligands, junctions in supramolecular polymers, and stabilizers for radical cations.     

Naphthalene Complexation by β-Cyclodextrin: Influence of Added Short Chain Branched and Linear Alcohols

Naphthalene forms 1 : 1 complexes with -cyclodextrin (-CD)in water. The binding constant is 377 ± 35 M^-1. Addition of linear or branched alcohols causes a reduction in the apparent strength of naphthalene binding (K_app) compared to the value in the absence of additives. For example, 1% 1-pentanol reduces K_app to 184 ± 31 M^-1. Branching does not alter K_app much for a given number of carbon atoms, e.g., it is 113 ± 9 M^-1for 2-pentanol and 116 ± 8 M^-1for 3-pentanol. The exception to this is tert-butanol for which K_app is 577 ± 40 M^-1. The variation in K_app as a function of [1-pentanol] yields values for the individual equilibrium constants contributing to K_app. This reveals that a ternary complex forms involving naphthalene, the CD and 1-pentanol. The constant for formation of the ternary complex is 99 ± 29 M^-2. NaI quenching of naphthalene fluorescence indicates that the CD cavity partially protects the naphthalene excited state fromthis water phase quencher. Interestingly, the Stern–Volmer constant is lower in the presence of 1-pentanol than in its absence, although there should be more unbound (and therefore more NaI accessible) naphthalene in the former system than in the latter. These apparently contradictory results are discussed in terms of ternary complex formation.     

Rapid on-chip postcolumn labeling and high-resolution separations of DNA

When performing genetic analysis on microfluidic systems, labeling the sample DNA for detection is a critical preparation step. Labeling procedures often involve fluorescently tagged primers and PCRs, which lengthen experimental run times and introduce higher levels of complexity, increasing the overall cost per analysis. Alternatively, on-chip labeling techniques based on intercalating dyes permit rapid labeling of DNA fragments. However, as noted in the literature, the stochastic nature of dye-DNA complex formation hinders the native electrophoretic migration of DNA fragments, degrading the separation resolution. In this study, we present a novel method of controllably labeling DNA fragments at the end of the electrophoretic separation channel in a glass microfluidic chip. Permitting the DNA to separate and labeling just before detection, achieves the rapid labeling associated with intercalators while maintaining the high resolution of native DNA separations. Our analyses are completed in minutes, rather than the hours typical of sample prelabeling. We demonstrate an electrophoretic microchip-based intercalator labeling technique that achieves higher resolution performance than reported in the literature to date.     

Imine insertion into a late metal-carbon bond to form a stable amido complex

An arylrhodium(I) complex containing a labile dative ligand was prepared, and its reactivity toward aryl imines was investigated. The arylrhodium(I) complex (DPPE)Rh(C5H5N)(p-tol), 2, was isolated in 65% yield from [(DPPE)Rh(mu-Cl)]2, pyridine, and p-tolyllithium. Reaction of 2 with the aldimine (p-tol)CH=N(C6H4-p-CO2Me) (3a-Tol) gave the Rh amide insertion product 4 in 88% isolated yield. The solid-state structure of 4 was determined by single-crystal X-ray diffraction. The reaction of 2 with the electron-neutral and electron-rich aldimines (Ph)CH=NPh (3b) and (p-tol)CH=N(C6H4-p-OMe) (3c) also appeared to involve insertion, but the amido complexes formed from these insertions were not stable. Thus, reaction of 2 with 3b, followed by addition of Et3NHCl, gave the amine and ketimine products (Ph)(p-tol)CH-NHPh, 5, and (p-tol)(Ph)C=N(Ph), 6, in 25% and 50% yields. Several lines of data indicate that these products are formed by a sequence of transformations involving insertion of imine to give a Rh amide intermediate, beta-hydrogen elimination, cyclometalation to form a bound imine and H2, and protonolysis of the metallacycle upon addition of Et3NHCl. Consistent with this proposal, the proposed metallacycle containing the ortho-metalated ketimine ligand (p-tol)2C=N(C6H4-p-OMe) was isolated and characterized by single-crystal X-ray diffraction.