Reaction of naphthalene‐2,3‐dicarbaldehyde with cyanide; A unique oxidative condensation product

Naphthalene‐2,3‐dicarbaldehyde (NDA), a reagent used for the fluorescent detection of amino acids in the presence of cyanide, self‐condenses in the presence of cyanide ion and methanol at room temperature to yield a unique crystalline product 2, 15‐hydroxybenzo[g]benzo[6,7]isochromeno[4,3‐c]isochromen‐7(15H)‐one. The product is proposed to result from facile air oxidation of NDA to a methyl ester in combination with benzoin condensation. Product 2 does not to form in the absence of air. The gHMBC spectrum of 2 distinguishes it from a possible alternative isomeric condensation product.     

Co‐oxidation of ammonia and ethanol in supercritical water,part 2: Modeling demonstrates the importance of H2NNOx

A co‐oxidation model was constructed from available submechanisms for ammonia and ethanol oxidation. The ammonia submechanism validated for combustion at atmospheric pressure conditions was modified for the higher densities and lower temperatures (655–700°C) of supercritical water. The ethanol submechanism had previously been tested and validated at supercritical water conditions. The initial model poorly reproduced experimental ammonia conversion data and was not able to consistently match nitrous oxide production as a function of temperature over a range from 655–700°C at 246 bar. To improve model predictions, the low‐pressure NH₂ + NO_x submechanism was replaced with a submechanism that included the H₂NNO_x adduct species that are expected to be stabilized in the high‐pressure supercritical water environment. Thermochemical and kinetic parameters for the adduct species were estimated with quantum chemical calculations using Gaussian 98 with the CBS‐Q method. The explicit treatment of the H₂NNO_x adducts resulted in nitrous oxide yield predictions that correctly reproduced experimental trends. This work represents a vital first step in improving the understanding of ammonia oxidation in supercritical water. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 653–662, 2008     

On-line nuclear orientation and relaxation studies of Cs isotopes

The hyperfine field of CsFe has been measured to be (+)40.8(0.7)T, using the technique of on-line low temperature nuclear orientation. The time dependent relaxation of¹²¹Cs^m Fe has also been investigated using a new technique, giving a Korringa constant C_k of 0.059 (15) sK. From this, an effective relaxation time of 3.0 (0.8)s can be deduced for the short lived¹¹⁸Cs^m(T_1/2=17s). This value has then been used to extract the magnetic moment of¹¹⁸Cs^m to be |μ|=5.4 (1.1) nm.     

Photoinduced Luminescence Blinking and Bleaching in Individual Single‐Walled Carbon Nanotubes

The temporal evolution of photoluminescence in individual single‐walled carbon nanotubes (SWNT) under strong laser irradiation is studied and pronounced blinking and bleaching is observed, caused by photoinduced oxidation that subsequently quenches mobile excitons. The nanotubes are isolated with sodium cholate and spun onto either a glass or mica surface. Their bleaching behavior is investigated for variable laser intensities in air and argon atmosphere. The decay rate for luminescence bleaching generally increases with higher laser intensity, however saturating on mica substrates, which is attributed to limited availability of oxygen in the vicinity of the nanotubes. Step‐like events in the luminescence time traces corresponding to single oxidation events are analyzed regarding relative step height and suggest an exciton diffusion range of about 105 nm.     

Calabi-Yau manifolds as complete intersections in products of complex projective spaces

We consider constructions of manifolds withSU(3) holonomy as embedded in products of complex projective spaces by imposing certain homogeneous holomorphic constraints. We prove that every such construction leads to one deformation class of manifolds withSU(3) holonomy. For a subset of these manifolds we prove simple connectedness, address the problem of calculating the second Betti number and explicitly calculate it for a class of constructions. This establishes a very wide class of manifolds withSU(3) holonomy, that can give rise to yet many more constructions via dividing out the action of suitably chosen discrete groups. Some of the examples studied may yield phenomenologically acceptable models.     

On effects of thickness on ductile crack growth in mild steel

Critical crack opening displacement (COD) values have been examined for a range of specimen thicknesses. The COD at the initiation of fracture δ₁ is found to be constant, given a plane-strain crack-tip stress-state, whereas the COD at maximum load δ_max decreases with increasing thickness. The loads required to produce instability are found to vary with thickness, in a way analogous to behaviour observed under linear elastic conditions. Crack growth under constant load for a range of specimen thicknesses has been examined, and failure has been found to occur at loads below that associated with Δ_max,; the minimum load per unit thickness required to cause failure decreasing with specimen thickness.