Accurate determination of pyridine-poly(amidoamine) dendrimer absolute binding constants with the OPLS-AA force field and direct integration of radial distribution functions

OPLS-AA force field and direct integration of intermolecular radial distribution functions (RDF) were employed to calculate absolute binding constants of pyridine molecules to amino group (NH2) and amide group hydrogen atoms in and first generation poly(amidoamine) dendrimers in chloroform. The average errors in the absolute and relative association constants, as predicted with the calculations, are 14.1% and 10.8%, respectively, which translate into ca. 0.08 and 0.06 kcal/mol errors in the absolute and relative binding free energies. We believe that this level of accuracy proves the applicability of the OPLS-AA, force field, in combination with the direct RDF integration, to reproducing and predicting absolute intermolecular association constants of low magnitudes (ca. 0.2-2.0 range).     

Synthesis and thermal characteristics of bisimides. I

Ten structurally different bisimide resins were prepared by reacting maleic anhydride/citraconic anhydride and benzophenone tetracarboxylic dianhydride with aromatic diamines and fused aromatic structures or heterocyclic groups. The amines included were 1,5-diaminonaphthalene, 2,5-bis(p-aminophenyl)1,3,4-oxadiazole, 3,3-bis(p-aminophenyl)phthalide, 9,9-bis(p-aminophenyl)fluorene. and 10,10-bis(p-aminophenyl)anthrone. These monomers were characterized by infrared (IR). ¹H-NMR, mass spectroscopy, and elemental analysis. Thermal polymerization of these monomers was investigated by differential scanning calorimetry. Broad exothermic peaks were observed for a temperature range of 225–380°C. Temperature of exothermic peak position was influenced by the presence of substituents at the olefinic bond, and in biscitraconimides it was 40–50°C lower than in the corresponding bismaleimides. Anaerobic char yields of cured bisimide resins ranged from 44 to 64%. Oxadiazole-containing bisimides had low thermal stability. Increase in formula weight between the imide groups did not influence the char yields in a systematic manner. Graphite cloth laminates with two of these bisimide resins were fabricated and tested for a number of physical properties. Their limiting oxygen index was 70–72%.     

Overview: recent progress in three-dimensional atom probe instruments and applications.

Over the last few years there have been significant developments in the field of three-dimensional atom probe (3DAP) analysis. This article reviews some of the technical compromises that have led to different instrument designs and the recent improvements in performance. An instrument has now been developed, based around a novel reflectron configuration combining both energy compensation and focusing elements, that yields a large field of view and very high mass resolution. The use of laser pulsing in the 3DAP, together with developments in specimen preparation methods using a focused ion-beam instrument, have led to a significant widening in the range of materials science problems that can be addressed with the 3DAP. Recent studies of semiconductor materials and devices are described.     

A direct synthesis of denbinobin

Denbinobin was made in seven steps from quinone 3. The cyclization of aldehyde 12 using P₄-tBu and the oxidation of a hindered alcohol with MnO₂ were key steps.     

A gas chromatographic determination of residues of eleven insecticides and two metabolites on olive tree leaves

A gas chromatographic (GC) method was developed and statistically validated for the simultaneous determination of residues of pyrethroid, endosulfan, and organophosphorus insecticides and some of their metabolites on olive tree leaves. Pesticide residues were extracted by static extraction with acetone-dichloromethane. After evaporation of the extract to dryness and redissolution in acetone, the organophosphorus insecticides were determined by GC with nitrogen-phosphorus detection. Another portion of the extract, after solvent change to acetonitrile, was cleaned up on an Alumina-N cartridge and analyzed for insecticides sensitive to electron-capture detection (ECD), i.e., pyrethroids and endosulfan and its metabolite. Recoveries of the organophosphorus insecticides ranged from 80.7 to 93.3% with relative standard deviations (RSDs) of < or = 7.2%; recoveries of the ECD-sensitive insecticides ranged from 71.6 to 89.5% with RSDs of < or = 11.6%. The method was used to analyze 26 samples of olive tree leaves from organic olive groves all over Greece, and the results confirmed the viability of the method for routine analysis. Residues of fenthion and fenthion sulfoxide were found in one and 3 samples, respectively, and their identities were confirmed by GC with mass spectrometry.     

Self-assembly of phosphate fluorosurfactants in carbon dioxide

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scatteringwas used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions.     

Synthesis of a model system for the preparation of phloroglucinol containing natural products

A model system for the synthesis of phloroglucinol containing natural products was synthesized. Key steps include a manganic acetate-mediated cyclization and the facile conversion of an alkene into a β-bromoenone.     

Complexation of aluminate anion by bis-tris in aqueous media at 25–50°C

Gibbsite, Al(OH)₃, solubility studies in aqueous NaCl solutions at pH 9 demonstrate that the aluminate anion forms a strong complex with the neutral Bis-tris molecule 2,2-Bis(hydroxymethyl)-2,2,2-nitrilotriethanol, at low temperatures. The logarithm of the molal concentration quotient for the reaction

Metallocycle synthesis accelerated by high pressure

Reaction of cis-[FeH₂(dmpe)₂](1) with diphenylbutadiyne results in an insertion into both of the iron-hydride bonds to form an iron metallocycle. Spectroscopic and crystallographic data of [Fe(PhHCC₂CHPh)(dmpe)₂] (3) show 1,4-diphenylbutatriene is symmetrically bound to the metal via the central double bond. The reaction to form the metallocyclic complex is greatly accelerated by application of external pressure. A 41% yield of (3) is isolated after two days at atmospheric pressure or after approximately 75 min at 800MPa.     

A new reaction of aryl aldehydes with aryl acetylenes in the presence of boron trihalides

[reaction: see text]. The reactions of aryl aldehydes with 2 equiv of arylacetylenes in the presence of boron trichloride yield (E,Z)-1,3,5-triaryl-1,5-dichloro-1,4-pentadienes. Reactions carried out in the presence of boron tribromide generate the corresponding (Z,Z)-1,3,5-triaryl-1,5-dibromo-1,4-pentadienes.