The spin- 1 2 singleton dipole

We establish a canonical formulation for a second-order wave equation for a spin-1/2field in a 3+2 de Sitter spacetime. We make variations of the Lagrangian, keeping the surface terms that appear in the process. By demanding that the surface terms be finite, we find that the second-order wave equation must be a singleton dipole equation. The resulting field theory exhibits a very interesting dynamics on the boundary. We study the Hamiltonian of the system and we discover that, after imposing the Lorentz condition, it reduces to an integral over a two-dimensional surface at spatial infinity.     

Mass spectrometry of heterocyclic compounds. VII—Evidence for common structure(s) of 1,2-benzisothiazole and benzothiazole molecular ions produced by electron-impact

1,2-Benzisothiazole and benzothiazole ion kinetic energy spectra, and metastable ion relative abundances of the same primary and secondary decomposition processes are compared. The results are interpretable as postulating slow (metastable) process(es) involving common structures and fast process(es)which are structurally dependent. Analogous indications are given by the interring H/D scrambling data, preceding the loss of DCN (or HCN) from 1,2-benzisothiazole-3-d₁ and benzothiazole-2-d₁ molecular ions, measured in either metastable or normal daughter ions at various electron beam energies.     

Comparison of three spectrophotometric methods for the determination of gamma-oryzanol in rice bran oil

A comparison of the results obtained by applying three spectrophotometric methods (at fixed wavelength, second-derivative and multicomponent analysis) to the determination of gamma-oryzanol in rice bran oil is reported.At fixed wavelength the results are more accurate when using isopropyl alcohol, rather than n-heptane, to dilute the oil samples, because the absorption bands of gamma-oryzanol are red-shifted and the absorbance, measured at lambda(max)=327 nm, is less affected by the interference of the oil "matrix" (lambda(max)=314 nm in n-heptane).However, to obtain accurate results also in oils with a low content of gamma-oryzanol, it is necessary to perform the analysis using second-derivative ((2)D330.365) or multicomponent (lambda=310-360 nm) methods. The first one fully removes the interference of oil matrix whilst the second, which needs a specific computational program to process the spectrophotometric data, furnishes evidence the presence of some unexpected interference in the analysis and/or standards which are not representative of the analysed samples, from the square root of the sum of the squared differences at each point between the linear combination of the standards and the unknown spectra (RMS error).Finally, some aspects of the chemical, spectroscopic (UV, IR) and thermoanalytical (TG, DSC) behaviour of gamma-oryzanol and the values of the parameters which enable "computation" of its UV spectra are reported.     

Thermodynamics of water/β-cyclodextrin system

The thermodynamics of β-cyclodextrin dehydration is investigated, by parallel DSC/TG experiments, on both fully and partially hydrated samples. The apparent dehydration enthalpies per mole of water are impossibly high and this fact suggests that another phenomenon, in addition to the rupture of the β-cyclodextrin/H₂O hydrogen bonds, contributes to the peak area. All the experimental evidence agrees with an ‘interaction model’ which assumes that deydration is accompanied by a slow and reversible rearrangement of the β-cyclodextrin structure.     

Supervised pattern recognition to discriminate the geographical origin of rice bran oils: a first study

Supervised pattern recognition appears to be a useful tool to authenticate foodstuffs according to their geographical or varietal origin, when a set of samples whose classification is known a priori are available. In this work, linear discriminant analysis and artificial neural networks trained by the back-propagation algorithm have been used to discriminate rice bran oils manufactured in three different countries (Italy, Thailand and Switzerland) according to their geographical origin. The variables to be included in the mathematical models have been chosen by means of Fisher F-ratio value among the chemical indices routinely determined on vegetable oils (particularly fatty acids, triglycerides and sterol composition). The prediction ability of all the classifiers was 100% as evaluated by cross-validation.     

New Spermine Alkaloids from Aphelandra tetragona (VAHL) NEES

18-O-Methylchaenorpine ( 1a ) and iso-18-O-methylchaenorpine ( 1b ) two novel stereoisomeric spermine alkaloids were isolated from the roots of Aphelandra tetragona (VAHL ) NEES. Their structures were established by chemical and spectroscopic studies.     

Triplet to ground state intersystem crossing and CIS-trans isomerization in stilbene

The T₁ ? S₀ intersystem crossing process in stilbene is considered adopting a formulation in which the isomerization coordinate can be treated separately. Energy surfaces in agreement with experimental and theoretical results are employed and pertinent spin-orbit coupling is evaluated. The calculated decay rate is in good agreement with the experimental results based on the azulene quenching effect. The qualitative feature that quantum yield for cis formation tends to be higher than the counterpart trans formation is explained. Deuterium effects are discussed and explanations for them are suggested.     

The ligand effect on the hydrolytic reactivity of Zn(II) complexes toward phosphate diesters

The catalytic effects of the Zn(II) complexes of a series of poliaminic ligands in the hydrolysis of the activated phosphodiesters bis-p-nitrophenyl phosphate (BNP) and 2-hydroxypropyl-p-nitrophenyl phosphate (HPNP) have been investigated. The reactions show first-order rate dependency on both substrate and metal ion complex and a pH dependence which is diagnostic of the acid dissociation of the reactive species. The mechanism of the metal catalyzed transesterification of HPNP has been assessed by solvent isotopic kinetic effect studies and involves the intramolecular nucleophilic attack of the substrate alcoholic group, activated by metal ion coordination. The intrinsic reactivity of the different complexes is controlled by the nature and structure of the ligand: complexes of tridentate ligands, particularly if characterized by a facial coordination mode, are more reactive than those of tetradentate ligands which can hardly allow binding sites for the substrate. In the case of tridentate ligands that form complexes with a facial coordination mode, a linear Br?nsted correlation between the reaction rate (log k) and the pK(a) of the active nucleophile is obtained. The beta(nuc) values are 0.75 for the HPNP transesterification and 0.20 for the BNP hydrolysis. These values are indicated as the result of the combination of two opposite Lewis acid effects of the Zn(II) ion: the activation of the substrate and the efficiency of the metal coordinated nucleophile. The latter factor apparently prevails in determining the intrinsic reactivity of the Zn(II) complexes.     

Synthesis of some substituted pyrido[1,2-a]pyrimidin-4-ones and 1,8-naphthyridines

The substituted 4H-pyrido[1, 2-a]pyrimidin-4-ones (I) were obtained by the condensation of substituted 2-aminopyridines with δ-ketocarboxylic esters in PPA. Some of the derivatives I were transformed into the corresponding 1, 8-naphthyridines II and III.     

Boundary effects and collisional activation in a quadrupole ion trap

The effects of storing ions at different values of the stability parameters a_z and q_zwere studied in a quadrupole ion trap, using helium or argon as buffer. A region was localized near the boundaries of the stability diagram in which the ions experience an increase in their kinetic energy. This is reflected in the occurrence both of fragmentation due to collisional activation and of a certain extent of ion loss due to unstable trajectories. The results of this excitation, referred to as ‘boundary effects,’ depend on the specific q_zat which the ion storage is performed and on the buffer gas used, and point to a simpler means of obtaining tandem mass spectra with the ion trap without the need to apply resonant tickle voltages between the end -cap electrodes.