Leaf anatomy affects the extraction of photosynthetic pigments by DMSO

Dimethylsulfoxide (DMSO) is a widely used solvent for the extraction of chlorophylls (Chls) from leaves of higher plants. The method is preferred because the time-consuming steps of grinding and centrifuging are not required and the extracts are stable for a long time period. However, the extraction efficiency of this solvent is not comparable among plant species, whereas the particular leaf anatomical characteristics responsible for this unevenness remain unknown. In order to examine the influence of leaf anatomy on the extraction efficiency of DMSO (i.e. the concentration of Chls extracted with DMSO as % of the concentration of Chls extracted with 80% acetone), leaves of 19 plant species with different anatomical characteristics were incubated for 40min in DMSO at 65 degrees C. Under these conditions, heterobaric leaves, which are characterized by the occurrence of bundle sheath extensions in the mesophyll, showed lower extraction efficiency of DMSO compared to homobaric leaves and conifer needles. Microscopical observations of DMSO incubated leaf tissues showed that bundle sheath extensions behave as anatomical barriers which prevent the diffusion of DMSO within heterobaric leaves, even after prolonged incubation with the solvent. The effect was stronger in heterobaric leaves possessing thick bundle sheath extensions. The extraction efficiency of DMSO in these leaves was improved by vacuum infiltration of the samples in the presence of warm (65 degrees C) solvent.     

Some physicochemical aspects of nanoparticulate magnetic iron oxide colloids in neat water and in the presence of poly(vinyl alcohol)

The preparation of magnetic iron oxide colloids directly from the coprecipitation of Fe (2+) and Fe (3+) species at different temperatures may lead to crystallites of higher size as the temperature of the reaction increases. On the other hand, dynamic light scattering investigations and dielectric measurements rather point to the similar colloidal size of the entities existing in their aqueous or solid-state dispersions, irrespective of the size of the primary nanocrystallites. Significant enhancement of the stability of the colloids, even in the presence of high electrolyte concentrations, is furnished after the addition of relatively small amounts of poly(vinyl alcohol), and the stabilization mechanism is discussed in terms of the various forces participating in the system. The experimental results suggest that the increased colloidal stability is triggered from the particles' decrease of velocity rather than from steric (entropic) effects originating from polymer absorption.     

Profiling and biomarker identification in plasma from different Zucker rat strains via high mass accuracy multistage mass spectrometric analysis using liquid chromatography/mass spectrometry with a quadrupole ion trap-time of flight mass spectrometer

High mass accuracy electrospray ionisation multistage tandem mass spectrometry (MS(n)) was applied to metabolite profiling studies on plasma samples derived from two strains of rat (the Zucker (fa/fa) obese strain and the normal wild type). Using a quadrupole ion trap time-of-flight (QIT-TOF) mass spectrometer, metabolite profiling software was applied to locate components of biological significance that could account for the differences between the two strains of rat and a formula prediction software tool was used to help identify individual components. The primary factor discriminating between the two populations was the concentration of endogenous lipids. In the Zucker (fa/fa) obese strain, the dominant ion signals and MS(n) spectra were in agreement with lysoglycerophosphocholine components such as palmitoyllysophosphatidylcholine, 1-oleoylglycerophosphocholine, 1-octadecyl-sn-glycero-3-phosphocholine and 1-stearoylglycerophosphocholine and these were found in relatively higher concentrations compared to the normal wild type. Components were identified using high mass accuracy MS(n) data, formula prediction software and by agreement with published mass spectra through internet databases, rather than using a conventional approach with authentic standards. This application shows that the use of high mass accuracy electrospray ionisation MS(n) together with a software tool can be used effectively to detect and characterise unknown analytes in complex matrices, and represents a promising approach for future profiling studies.     

Correlating Structure and KA2 Catalytic Activity of ZnII Hydrazone Complexes

Two new Zn(II) complexes bearing tridentate hydrazone-based ligands with NNO or NNS donor atoms were synthesised and characterised by elemental analysis, infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies, and single crystal X-ray diffraction methods. These complexes, together with four previously synthesised analogues, having hydrazone ligands with a NNO donor set of atoms, were successfully employed as catalysts in the ketone-amine-alkyne (KA²) coupling reaction, furnishing tetrasubstituted propargylamines, compounds with unique applications in organic chemistry. DFT calculations at the CAM-B3LYP/TZP level of theory were performed to elucidate the electronic structure of the investigated Zn(II) complexes, excellently correlating the structure of the complexes to their catalytic reactivity.     

Photooxygenation of Furylalkylamines: Easy Access to Pyrrolizidine and Indolizidine Scaffolds

A highly adaptable method targeting the ubiquitous and very important pyrrolizidine and indolizidine scaffolds is presented. The general synthetic utility of the method is underscored by its application to the rapid and easy synthesis of five natural products starting from readily accessible alkylfuran precursors. These unprotected primary furylalkylamines are subjected to photooxygenation conditions, which initiate a complex cascade reaction sequence concluding with the production of high value motifs. This sequence can be tailored to need by varying the choice of both photosensitizer and base additive.     

Darboux Transformation for the Vector Sine-Gordon Equation and Integrable Equations on a Sphere

We propose a method for construction of Darboux transformations, which is a new development of the dressing method for Lax operators invariant under a reduction group. We apply the method to the vector sine-Gordon equation and derive its Bäcklund transformations. We show that there is a new Lax operator canonically associated with our Darboux transformation resulting an evolutionary differential-difference system on a sphere. The latter is a generalised symmetry for the chain of Bäcklund transformations. Using the re-factorisation approach and the Bianchi permutability of the Darboux transformations, we derive new vector Yang–Baxter map and integrable discrete vector sine-Gordon equation on a sphere.     

Using singlet oxygen to synthesise a [6,6,5]-bis-spiroketal in one-pot from a simple 2,5-disubstituted furan

Singlet oxygen (1O2) proves to be a powerful tool in mediating the one-pot synthesis of a salinomycin-type [6,6,5]-bis-spiroketal unit starting from a suitably substituted furan nucleus.     

Characterization of the core-shell nanoparticles formed as soluble hydrogen-bonding interpolymer complexes at low pH

The formation of soluble hydrogen-bonding interpolymer complexes between poly(acrylic acid) (PAA) and poly(acrylic acid-co-2-acrylamido-2-methyl-1-propane sulfonic acid)-graft-poly(N,N-dimethylacrylamide) (P(AA-co-AMPSA)-g-PDMAM) at pH=2.0 was studied. A viscometric study showed that in semidilute solution a physical gel is formed due to the interconnection of the anionic P(AA-co-AMPSA) backbone of the graft copolymer, in a transient network, by means of the complexes formed between the PDMAM side chains of the graft copolymer and PAA. Dynamic and static light scattering measurements, in conjunction with small-angle neutron scattering measurements, suggest the formation of core-shell colloidal nanoparticles in dilute solution, comprised by an insoluble PAA/PDMAM core surrounded by an anionic P(AA-co-AMPSA) corona. Even if larger clusters are formed in semidilute solution, the size of the insoluble core remains practically stable. Atomic force microscopy performed under ambient conditions reveal that the particles collapse and flatten upon deposition on a substrate, with dimensions close to the ones of the dry hydrophobic core.     

Investigation of the incorporation of electrolyte anions in porous anodic Al2O3 films by employing a suitable probe catalytic reaction

A new method has been developed capable of describing the incorporation of electrolyte anions along the pore wall surface and across both the barrier layer and the pore wall oxide after the establishment of the steady state of growth of porous anodic Al₂O₃ where other methods cannot be applied to obtain reliable results. The knowledge of the nature/composition of anodic oxides as regards the incorporation of species like electrolyte anions is of specific importance for both the understanding of the electrochemical mechanism of oxide production and growth and the scientific and technological applications of porous anodic Al₂O₃ films. The method consists of the selection and use of a suitable catalytic probe reaction on porous anodic oxides at thicknesses varying from a value near zero up to the maximum limiting thickness and the treatment of the experimental reaction rate results by a properly developed mathematical formalism. This method was employed in anodic Al₂O₃ films prepared in H₂SO₄ anodizing electrolyte at a constant bath temperature and different current densities using as a probe reaction the decomposition of HCOOH on these oxides, which is almost exclusively a dehydration reaction, at relatively high reaction temperatures, 350 °C and 390 °C, where the effect of other species except SO₄ ²⁻ incorporated in the oxide on the reaction rate is eliminated. It has been shown that the fraction of the intercrystallite surfaces occupied by SO₄ ²⁻ follows a parabola-like distribution. It has a significant value at the pore base surface, depending on the current density, then it passes through a maximum along the pore wall surface and across both the barrier layer and the pore walls near the pore bases at positions depending on the current density and then becomes almost zero at the mouths of the pores of the oxide with the maximum limiting thickness and at both the Al₂O₃/Al interface and cell boundaries. The maximum value of the surface coverage is almost independent of the current density and is always near 1, showing an almost complete saturation of intercrystalline surfaces at these positions. The above distribution of surface coverage predicts a qualitatively similar distribution of the SO₄ ²⁻ bulk concentration across both the barrier layer and pore wall oxide around the pore bases. The method may be improved and developed further either for a more detailed investigation of the above films or to investigate films prepared in other pore-forming electrolytes. Received: 30 July 1998 / Accepted: 30 September 1998