Tetra-t-butyl magnesium phthalocyanine on gold: electronic structure and molecular orientation

In this work we have investigated the electronic structure and the molecular orientation of (t-Bu)(4)PcMg (tetra-t-butyl magnesium phthalocyanine) on polycrystalline and single crystalline gold substrates using photoemission spectroscopy and x-ray absorption spectroscopy, and we compare the results to the unsubstituted PcCu (copper phthalocyanine). The C 1s photoemission spectrum is described similar to unsubstituted relatives with an additional component for the aliphatic substituents. The variation of the excitation energy causes distinct differences in the shape of the C 1s spectrum, which is very useful for the analysis of the molecular orientation in the uppermost layer. It is shown that despite of the sterically demanding substituents, ordered sublimed films of (t-Bu)(4)PcMg are accessible, the orientation of the molecules, however, is different from the orientation of the unsubstituted relatives.     

Immunological and biochemical evidence that blepharismin is not a prosthetic group

A polyclonal, multispecific antiserum was raised against a whole 3[(3-cholamidopropyl)-dimethylammonio]-1-propanesulfonate-extract of nonirradiated Blepharisma japonicum cells. It was used to reveal the composition of solutions that were hypothesized to contain the photoreceptor of the ciliate. A Bio-Gel A 1.5 m fine column chromatography of the extract allowed recovery of a single elution peak isolated by recording the 580 nm light absorbance. Fused-rocket immunoelectrophoresis of this material revealed a large number of > 300 kDa coeluted proteins. Blepharismin-rich material with a molecular mass of approximately 50 kDa, consisting of at least nine proteins was obtained when the same extract underwent preparative isoelectric focusing before column chromatography separation. Purification of the pigment obtained from light-exposed cells gave blepharismin-rich material with a molecular weight of approximately 200 kDa. Comparison of the materials obtained under the same conditions, either from the dark-kept or light-irradiated cells, by means of pore-gradient electrophoresis confirmed that proteins present in the two preparations were different. It revealed only a very small amount, if any, of proteins in the chromatography fractions with the highest absorbance at 600 nm. Results are discussed on the basis of the hypothesis that a specific blepharismin-binding protein does not exist in the protozoan.     

Total synthesis of a conformationally constrained didemnin B analog

The total synthesis of a didemnin B analogue containing a conformationally constrained replacement for the isostatine moiety is reported. Synthetic highlights include an improved preparation of 2-hydroxy-3-cyclohexenecarboxylic acid and a new strategy for accessing the macrocycle.     

Determination and confirmation of malachite green and leucomalachite green residues in salmon using liquid chromatography/mass spectrometry with no-discharge atmospheric pressure chemical ionization

A liquid chromatography/mass spectrometry (LC/MS) method was developed to quantitate and confirm residues of leucomalachite green (LMG) in salmon tissue after their conversion to chromic malachite green (MG) in the extraction process. The method uses no-discharge atmospheric pressure chemical ionization (APCI) in conjunction with an ion-trap instrument to generate product-ion spectra. In the sample preparation procedure, salmon tissue is extracted with acetonitrile/buffer, the LMG residue is partitioned into methylene chloride, the LMG is converted to MG using an organic oxidizing agent, and the MG is isolated on alumina/propylsulfonic acid solid-phase extraction cartridges. The method was validated by fortifying salmon with different levels of LMG, and then detecting the residue as MG The LC/MS conditions, including a comparison of electrospray and no-discharge APCI, were evaluated and optimized. MG was not confirmed in any of the control tissue extracts, and all fortified samples analyzed during validation met the confirmation criteria as described. In addition to providing confirmatory data, this method can provide an alternative method for quantitation of MG in salmon. The recoveries of LMG measured as MG by this LC/MS method, at fortification levels of 1-10 ng/g were very high (86-109%), with low relative standard deviation(RSD) values (6.4-13%). The results agreed very closely with those obtained for the same extracts using an LCNIS procedure, indicating that matrix suppression was not an issue. The presence of LMG in salmon tissue samples fortified at 0.25 ng/g was confirmed by this method, with an average recovery of 70.1% and an RSD of 12.0%. Sample extracts from fish exposed to MG were also analyzed.     

Study on the stability of noradrenaline and on the determination of its acidity constants

Noradrenaline is a catecholamine which has been largely recognised to play a very important role in biological systems. In view of the neurotransmitter's alleged importance, this work aimed at showing the influence of time on its spectral behaviour using different analytical methods and determining its acidity constants through spectrophotometric titration and by the so-called point-by-point analysis, where the samples are freshly prepared for each pH value investigated at the instant required. Because the catecholamines are light-sensitive and likely to react with the oxygen in the surrounding air, both methods used preclude its incidence onto the samples being analysed under the presence of a nitrogen atmosphere maintained over the solutions. The constants obtained through point-by-point analysis were log beta1 = 30.71+/-0.16, log beta2 = 22.00+/-0.15 and log beta3 = 11.69+/-0.16.     

Oils from Wild,Micropropagated Plants,Calli, and Suspended Cells ofEuphorbia characias L.

Applied Biochemistry and Biotechnology - Micropropagated Euphorbia characias plants gave higher yields of crude oil than did wild ones. Leaves of either wild and micropropagated plants contained...     

Complexation of the Non-steroidal Anti-inflammatory Drug Nabumetone with Modified and Unmodified Cyclodextrins

The inclusion of the anti-inflammatory drug, Nabumetone, in -, - and hydroxypropyl--cyclodextrin (CDs) is studied using UV-VIS absorption and steady-state fluorescence emission. Binding constants and thermodynamic parameters of complex formation are determined by spectrofluorimetry. The inclusion phenomena of Nabumetone with the three cyclodextrins is compared with that of the well known similar anti-inflammatory drug Naproxen. In the case of Nabumetone pronounced differences are observed in the complexation process with each cyclodextrin whereas the respective Naproxen complexes are nearly identical. ¹H-NMR experiments show that the inclusion process in Nabumetone can occur either through the substituents in the -2 (butanone) or -6 (methoxy) positions in the naphthalene ring.     

The existence of ferrous ferricyanide

Evidence in the literature on the synthesis of ferrous ferricyanide is critically discussed. Pyrolysis and pressure effects on Prussian Blue lead to ferrous ferrocyanide together with decomposition by-products, and not to ferrous ferricyanide. The latter compound could be a precursor in the formation of Turnbull's Blue or an excited state of Prussian Blue, but it is not a stable chemical species.     

Kinematical and gravitational analysis of the rocket-borne clock experiment by Vessot and Levine using the revised Robertson's test theory of special relativity

The kinematic aspects of the rocket-borne clock experiment by Vessot and Levine are analyzed with the revised Robertson's test theory of special relativity (Found. Phys. 14, 625 (1984)). Besides the expected time-dilation, it is found that the intermediate steps of this experiment yield in principle Michelson-Morley type information (a relation between longitudinal and transverse length contractions) in the third order of the velocities involved, but no relativity-of-simultaneity related effects.The flat space-time test theory induces a family of spherically symmetric line elements that become the Schwarzschild line element in the relativistic case and also in theabinito rest frame of the theory. These line elements represent the same space-time manifold, but pertain in a one-to-one correspondence to the different flat space-time coordinate transformations of the test theory. The conserved energy is related to the family of local energies in the tangent plane. No deviations from the orthodoxy appear at the pertinent levels of approximation. Hence the unexplained residuals of the Vessot-Levine experiment are not due in obvious ways to kinematic and gravitational frequency shifts caused by deviations of the real coordinate transformations from the Lorentz transformations.This work was started while the author was at Departamento de Fisica, Facultad Experimental de Ciencias, Universidad del Zulia, Maracaibo, Venezuela. It was completed at the Department of Physics, Utah State University, Logan, Utah 83422.