Particle-rod hybrids: growth of arachidic acid molecular rods from capped cadmium selenide nanoparticles

This communication describes a spin-coating method to nucleate organic molecular rods of uniform size from an inorganic nanoparticle at a solid surface. The particle-rod hybrid structure spontaneously forms when a film is spin coated from a mixed 2-propanol solution of arachidic acid (AA) and nanoparticles of cadmium selenide capped by mercaptoundecanoic acid (MUA-CdSe) on graphite. AFM images show that MUA-CdSe nanoparticles nucleate single crystalline rods of AA with a cross section of a single unit cell of the C-form. The solution-based process potentially allows the precise tuning of the wetting profile of the solution on the surface-attached nanoparticle, which provides the reservoir for the growth of the single crystalline rods. The results suggest that nanoparticles can be regarded as nanoseeds for the nucleation of guest crystals. It should be possible to further functionalize the AA rods by electrostatic complexation with metal or organic ions.     

Alternating structures in copolymers as elucidated by microozonolysis

The technique of microozonolysis followed by gas chromatography has been used to determine the amount of 1,2-structures occurring as 1,4–1,2–1,4 sequences in n-butyl-lithium-initiated polybutadienes. The product obtained from the ozonolysis of these sequences, 3-formly-1,6-hexanedial, was directly proportional to the 1,2 (vinyl) content of the polymers as measured by infrared or NMR spectroscopy. An unusual ozonolysis product, 4-octene-1,8-dial, has been found in the ozonolysis products of high-1,4 poly-butadienes. Ozonolysis has also been used to determine alternating structures in propylene-butadiene copolymers. The product obtained from ozonolysis of such structures is 3-methyl-1,6-hexanedial. Ozonolysis of a polyisoprene containing equal amounts of 1,4 and 3,4 structures indicated it to have a nonalternating structure with long blocks of 1,4-isoprene units. Gas chromatographic separation was accomplished by using sucrose acetate isobutyrate with Carbowax 20M as the liquid phase. Retention times were established by using model compounds where possible.     

The correlation of NMR chemical shifts with EHT calculated electron densities for 3-pyridinols

The NMR spectra of a series of five 3-pyridinols in dioxane and dimethyl sulfoxide have been correlated with electron densities calculated by the Extended Hückel MO method. The data were found to fit a straight line of the form y=ax+b. The effects of hydrogen-bonding between pyridinol molecules on the correlation have been considered, and they have been estimated quantitatively for 6-methyl-3-pyridinol via Extended Hückel Calculations on a hydrogen-bonded model.

---

Zusammenfassung Die Kernresonanzspektren von fünf 3-Pyridinolen in Dioxan und Dimethylsulfoxyd wurden mit den Elektronendichten aus dem erweiterten Hückelverfahren korreliert, und zwar ergibt sich eine lineare Beziehung. Der Einfluß von intermolekularen Wasserstoffbrücken ist für einen Fall (die 6-Methyl-Verbindung) durch EHT-Rechnungen festgestellt und in den übrigen Fällen geschätzt worden.

---

Résumé Les spectres NMR d'une série de cinq 3-pyridinols dans le dioxane et le diméthyle-sulfoxyde ont été corrélés avec les densités électroniques calculées par la méthode de Hückel Etendue. Les données se placent correctement sur une droite y=ax+b. Les effets de la liaison hydrogène entre les molécules de pyridinol ont été envisagés et estimés quantitativement pour le 6-méthyl-3-pyridinol par des calculs EHT sur un modèle à liaison hydrogène.

     

Comparison of fingerprint-based methods for virtual screening using multiple bioactive reference structures

Fingerprint-based similarity searching is widely used for virtual screening when only a single bioactive reference structure is available. This paper reviews three distinct ways of carrying out such searches when multiple bioactive reference structures are available: merging the individual fingerprints into a single combined fingerprint; applying data fusion to the similarity rankings resulting from individual similarity searches; and approximations to substructural analysis. Extended searches on the MDL Drug Data Report database suggest that fusing similarity scores is the most effective general approach, with the best individual results coming from the binary kernel discrimination technique.     

Liberation of pnicogen chains from Cu(2)P(1.8)As(1.2)I(2): synthesis and characterization of a new allotrope of P--As

Removal of CuI from Cu(2)P(1.8)As(1.2)I(2) results in a novel P--As allotrope. Although the product is X-ray amorphous, lattice fringes are observed in the transmission electron micrographs with spacings reflecting the diameter of the linear pnicogen polymer in Cu(2)P(1.8)As(1.2)I(2), suggesting the pnicogen chains remain intact upon loss of CuI. The straight needles present in Cu(2)P(1.8)As(1.2)I(2) appear to be kinked in the P--As phase due to lattice mismatch between the liberated polymers, ultrasonic treatment, or a combination of these effects. This new P--As modification is semiconducting with a band gap of 1.05 eV.