Engineering the structure and magnetic properties of crystalline solids via the metal-directed self-assembly of a versatile molecular building unit

We report the supramolecular chemistry of several metal complexes of N-(4-pyridyl)benzamide (NPBA) with the general formula [Ma(NPBA)2AbSc], where M = Co2+, Ni2+, Zn2+, Mn2+, Cu2+, Ag+; A = NO3-, OAc-; S = MeOH, H2O; a = 0, 1, 2; b = 0, 1, 2, 4; and c = 0, 2. NPBA contains structural features that can engage in three modes of intermolecular interactions: (1) metal-ligand coordination, (2) hydrogen bonding, and (3) pi-pi stacking. NPBA forms one-dimensional (1-D) chains governed by hydrogen bonding, but when reacted with metal ions, it generates a wide variety of supramolecular scaffolds that control the arrangement of periodic nanostructures and form 1- (2-4), 2- (5), or 3-D (6-10) solid-state networks of hydrogen bonding and pi-pi stacking interactions in the crystal. Isostructural 7-9 exhibit a 2-D hydrogen bonding network that promotes topotaxial growth of single crystals of their isostructural family and generates crystal composites with two (11) and three (12) different components. Furthermore, 7-9 can also form crystalline solid solutions (M,M')(NPBA)2(NO3)2(MeOH)2 (M, M' = Co2+, Ni2+, or Zn2+, 13-16), where mixtures of Co2+, Ni2+, and Zn2+ share the same crystal lattice in different proportions to allow the formation of materials with modulated magnetic moments. Finally, we report the effects that multidimensional noncovalent networks exert on the magnetic moments between 2 and 300 K of 1-D (4), 2-D (5), and 3-D (7, 8, 10, and 13-16) paramagnetic networks.     

Origin of the acidity enhancement of formic acid over methanol: resonance versus inductive effects

Density functional theory calculations were employed to study the relative contribution of resonance versus inductive effects toward the 37 kcal/mol enhanced gas-phase acidity (DeltaH degrees (acid)) of formic acid (1) over methanol (2). The gas-phase acidities of formic acid, methanol, vinyl alcohol (5), and their vinylogues (6, 8, and 9) were calculated at the B3LYP/6-31+G level of theory. Additionally, acidities were calculated for the formic acid and vinyl alcohol vinylogues in which the formyl group and the vinyl group, respectively, were perpendicular to the rest of the conjugated system. Comparisons among these calculated acidities suggest that inductive effects are the predominant effects responsible for the enhanced acidity of formic acid over methanol, accounting for between roughly 62% and 65% of the total enhanced acidity; the remaining 38% to 35% of the acidity enhancement appears to be due to resonance effects. Further comparisons suggest that resonance effects are between roughly 58% and 65% of the 26 kcal/mol calculated acidity enhancement of vinyl alcohol over methanol, and the remaining 42% to 35% are due to inductive effects.     

An alternative multipolar expansion for intermolecular potential functions

We have derived a new multipolar expansion for intermolecular potential-energy functions with applications in molecular physics, theoretical chemistry, and mathematical physics. The new formulation employs a separation of radial and angular terms with a simple index structure that leads to computational efficiency and ease of physical interpretation. For the case of the Coulomb interaction, we compare the present formulation with two conventional multipole expansions: the Cartesian tensor and the irreducible spherical tensor expansions. The new formalism leads to efficient numerical algorithms that are useful for general applications beyond intermolecular potentials. In addition to the electrostatic Coulomb interaction, we illustrate the formalism with applications to special function theory and a bipolar expansion involved in potential theory.     

Electrophilic lactonization as a tool in acyclic stereocontrol. Synthesis of serricornin

Several electrophilic lactonization procedures have been explored as a means of functionalizing olefinic carboxylic acids with relative asymmetric induction, Iodolactonization of δ,? -unsaturated acids under conditions of thermodynamic control exhibits good 1,2- and 1,3-, but not 1,4-induction in the formation of δ-lactones. Mercurilactonization proceeds with good stereocontrol in the formation of both γ- and δ-lactones (1,2-induction), but suffers from the difficulty of elimination during reductive demercuration; phenylselenolactonization with N-(phenylseleno)phthalimide is apparently kinetically controlled, affording high induction with 10, a strongly sterically biased substrate leading to a δ-lactone, but not with 16, which leads to a γ-lactone. In contrast, hydroxymethyllactonization proceeds with good stereocontrol in the case of 26, the ester of 10, but not with the analogous ester of 16. The lactones resulting from cyclization of 10 and 13 were converted in stereospecific fashion into each of the stereoisomers of(±)-serricornin.     

Thin chip microsprayer system coupled to quadrupole time-of-flight mass spectrometer for glycoconjugate analysis

A thin chip polymer-based microsprayer has been coupled to a hybrid quadrupole time-of-flight mass spectrometer (QTOF MS) and introduced in carbohydrate research. The feasibility of the approach is demonstrated for mapping, sequencing and structural elucidation of glycoconjugates originating from human body fluids and tissues such as a glycopeptide mixture from normal human urine and an isolated and purified GT1 ganglioside fraction from normal adult human brain. The optimization procedure required by each glycoconjugate category is described and the advantages of the system in terms of flexibility and adaptability to QTOF MS, stability of the ESI MS signal, carbohydrate ionization and sequencing, sensitivity, speed of analysis and sample consumption are discussed.     

Syntheses of reactive fluorescent stains derived from 5(2)-aryl-2(5)-(4-pyridyl)oxazoles and bifunctionally reactive linkers

Several bifunctionally reactive linkers containing halide or sulfonate ester groups were prepared. The linkers were used to quaternize 5-(4-methoxyphenyl)-2-(4-pyridyl)oxazole and 2-(6-chromanyl)-5-(4-pyridyl)oxazole to produce fluorescent stains that contained a reactive group such as an isothiocyanate, an N-hydroxysuccinimidyl ester, a maleimide, or an oxirane. The stains were derivatized with either 1-propylamine, 1-propanethiol, or piperidine, as appropriate, to help in characterization. The stains may serve as more photostable alternatives to fluoresceins or coumarins.     

The existence of non-topological solitons in the self-dual Chern-Simons theory

In the recently discovered (2+1)-dimensional relativistic Chern-Simons model, self-duality can be achieved when the Higgs potential density assumes a special form for which both the asymmetric and symmetric vacua are ground state solutions. This important feature may imply the coexistence of static topological and non-topological vortex-like solutions inR ² but the latter have been rather elusive to a rigorous construction. Our main purpose in this paper is to prove the existence of non-topological radially symmetricN-vortex solutions in the self-dual Chern-Simons model. By a shooting method, we obtain a continuous family of gauge-distinctN-vortex solutions. Moreover, we are also able to classify all possible bare (or 0-vortex) solutions.     

A new strategy for the construction of the imidazo[1,5-a]quinoxalin-4-one ring system and its application to the efficient synthesis of BMS-238497, a novel and potent Lck inhibitor

A new efficient strategy was developed for the construction of the imidazo[1,5-a]quinoxalin-4-one ring system. The new method involves condensation of o-nitroaniline with glyoxylate in methanol followed by treatment of the resulting alpha-(o-nitroanilino)-alpha-methoxy acetate with tosylmethyl isocyanide (TosMIC) reagent to give 1-(o-nitrophenyl)imidazole-5-carboxylate. Reductive cyclization of the nitro imidazole carboxylate afforded imidazo[1,5-a]quinoxalin-4-one in three steps and 60% overall yield. The new method was successfully applied to the synthesis of BMS-238497, a novel and potent Lck inhibitor.     

Aerobic catalytic photooxidation of olefins by an electron-deficient Pacman bisiron(III) mu-oxo porphyrin

The synthesis and oxygen atom transfer (OAT) photoreactivity of a diiron(III) mu-oxo meso-tripentafluorophenyl bisporphyrin appended to a dibenzofuran spacer are presented. Reaction of 4,6-diformyldibenzofuran under standard Lindsey conditions furnishes the parent cofacial porphyrin architecture in a single step. These cofacial porphyrins photocatalyze the oxidation of sulfides and olefins using visible light and molecular oxygen as the terminal oxidant. High turnover numbers reflect the enhanced stability of the electron-deficient diiron(III) mu-oxo bisporphyrin core appended to a dibenzofuran spacer under aerobic conditions.     

The effect of amino acid deletions and substitutions in the longest loop of GFP

Background  

The effect of single and multiple amino acid substitutions in the green fluorescent protein (GFP) from Aequorea victoria has been extensively explored, yielding several proteins of diverse spectral properties. However, the role of amino acid deletions in this protein -as with most proteins- is still unknown, due to the technical difficulties involved in generating combinatorial in-phase amino acid deletions on a target region.