Shaping of gelling biopolymer drops in an elongation flow

Shaping, defined as deformation in combination with gel formation of gelatine and kappa-carrageenan drops in an elongation flow, was studied. The focus was to investigate the possibility of shaping and fixating small drops in the diameter range 20 to 229 mum. In the shaping progress and the influence of experimental properties, the viscosity, temperature, and flow of the deforming fluid were examined on the final drop shape. In the experiments a hot emulsion of an aqueous biopolymer solution in silicone oil was injected into cold silicone oil where a deforming elongation flow field existed. After injection, a temperature decrease in the drops resulted in a gel formation of the biopolymer and a fixation of the deformed drop in the flow. The shape was measured and the effect on the drop aspect ratio was determined by image analysis. Over the total drop diameter range, kappa-carrageenan was more ellipsoid-shaped than gelatine, with a maximum aspect ratio of 6 compared to 4 for gelatine. For small drops, around 22 mum, it is possible to shape kappa-carrageenan, but for gelatine small drops tend to be unaffected. An increase in viscosity, temperature, and flow resulted in an increase in the final fixated shape of the drops. The differences in drop deformation between the biopolymers were explained by drop-viscosity/oil differences and differences in the kinetics of gel formation. The different gel formation kinetics resulted in a short, well-defined, shaping process for kappa-carrageenan, while for gelatine the process was more complex, with both deformation and relaxation present at different stages.     

A Theoretical Study of LiHe+ n , NaHe+ n , and MgHe+ n Complexes, with n=1, 2, 3, 4

The LiHe⁺ _n , the NaHe⁺ _n , and the MgHe⁺ _n complexes with n=1, 2, 3, 4 were studied using ab initio calculations with the MP2/6-311+G(3df, 3pd) method. The complexes are found to be stable. For the n=1 complexes, previous results were available and the calculations performed are in good agreement with those results. This lends credibility to the results obtained for the complexes with higher n.     

Enantioselective carbolithiation initiated cascade reactions

Enantioselective cascade reactions are very powerful synthetic protocols for the assembly of complex architectures. Our current approach is to exploit a (-)-sparteine-controlled enantioselective carbolithiation of 2-propenylarylamines to provide chiral intermediates, which depending upon choice of electrophile are subsequently in situ converted into products of increasing complexity. The chiral center, formed in high enantiomeric ratio in the first carbolithiation step, is carried through the cascade reaction sequence to the final products and is independent of electrophile used. The scope of the cascade reaction is outlined in terms of reaction conditions, alkyllithiums, and electrophiles.     

Bacterial iron transport: coordination properties of azotobactin, the highly fluorescent siderophore of Azotobacter vinelandii

Azotobacter vinelandii, a nitrogen-fixing soil bacterium, secretes in iron deficiency azotobactin delta, a highly fluorescent pyoverdin-like chromopeptidic hexadentate siderophore. The chromophore, derived from 2,3-diamino-6,7 dihydroxyquinoline, is bound to a peptide chain of 10 amino acids: (L)-Asp-(D)-Ser-(L)-Hse-Gly-(D)-beta-threo-HOAsp-(L)-Ser-(D)-Cit-(L)-Hse-(L)-Hse lactone-(D)-N(delta)-Acetyl, N(delta)-HOOrn. Azotobactin delta has three different iron(III) binding sites which are one hydroxamate group at the C-terminal end of the peptidic chain (N(delta)-Acetyl, N(delta)-HOOrn), one alpha-hydroxycarboxylic function in the middle of the chain (beta-threo-hydroxyaspartic acid), and one catechol group on the chromophore. The coordination properties of its iron(III) and iron(II) complexes were measured by spectrophotometry, potentiometry, and voltammetry after the determination of the acid-base functions of the uncomplexed free siderophore. Strongly negatively charged ferric species were observed at neutral p[H]'s corresponding to a predominant absolute configuration Lambda of the ferric complex in solution as deduced from CD measurements. The presence of an alpha-hydroxycarboxylic chelating group does not decrease the stability of the iron(III) complex when compared to the main trishydroxamate siderophores or to pyoverdins. The value of the redox potential of ferric azotobactin is highly consistent with a reductive step by physiological reductants for the iron release. Formation and dissociation kinetics of the azotobactin delta ferric complex point out that both ends of this long siderophore chain get coordinated to Fe(III) before the middle. The most striking result provided by fluorescence measurements is the lasting quenching of the fluorophore in the course of the protonation of the ferric azotobactin delta complex. Despite the release of the hydroxyacid and of the catechol, the fluorescence remains indeed quenched, when iron(III) is bound only to the hydroxamic acid, suggesting a folded conformation at this stage, around the metal ion, in contrast to the unfolded species observed for other siderophores such as ferrioxamine or pyoverdin PaA.     

Tricoordinated phosphorus-containing macrocycles: New synthetic strategies

Phosphorus dialdehydes RP (OC₆H₄CHO)₂ (R = Ph, Me₂N) react with phosphodihydrazides PhP(Y)-[N(CH₃)NH₂]₂ (Y = S, O) to give macrocycles 6a–c arising from [2 + 2] cyclocondensation reactions. Treatment of phosphodihydrazone PhP(S) [OC₆H₄CH N–N(Me)H]₂ 7 with phenyldichlorophosphine affords macrocycle 8 possessing tri and tetracoordinated phosphorus atoms. Clean desulfurization of thiophosphorus macrocycles 9 and 12 gives rise selectively to new tricoordinated phosphorus containing macrocycles 11 and 13 .     

Concentration polydispersity in polymer gels

For swollen polymer networks there is no generally accepted relation between the macroscopic osmotic properties and the scattering behaviour. Detailed information on the relationship between these properties can, however, be deduced from complementary measurements of osmotic and elastic behaviour, small angle neutron and X-ray scattering (SANS and SAXS) and quasi-elastic light scattering. We describe such an investigation in two types of networks, differing in the mechanism of cross-linking. The SANS spectra yield information on the structure, which is generated both by the dynamics of the system and by long range static constraints. The former, arising from thermodynamic concentration fluctuations, governs the macroscopic osmotic and elastic moduli of the swollen network. The static superstructure in the gel reflects local variations in the cross-link density. The resulting concentration polydispersity, <δφ²>/φ², is determined by the details of the cross-linking procedure. Its concentration dependence as a function of gel swelling can be expressed in terms of the same macroscopic osmotic and elastic variables as those that govern the thermodynamic properties of the gel.     

Phosphorus-Containing Dendrimers: Synthesis and Properties

Several series of phosphorus-containing dendrimers have been designed to study the variation of their properties, depending on the type, the location (surface, branches, core, and cavities), and the number of functions implied.     

Hydrogen Migration and Reductive Elimination of Alkyne in Fe(CO)4 P(tBu) (C °CPh)H Induced by the Action of Co2 (CO)8

Abstract

One of the possible ways of getting phosphacumulene complexes could be the complexation of phosphinoalkynes, which might induce the migration of hydrogen from phosphorus to the β carbon of the alkynyl group.     

[HFe(CO)4 – A Versatile Reagent toward Dichlorophosphines,Phosphenium Salts,Phospha-alkenes and Diphosphenes

Abstract

A new entry to non classical phosphorus complexes is reported.     

Photoresponsive supramolecular systems: self-assembly of azodibenzoic acid linear tapes and cyclic tetramers

A new strategy to effect photoinduced control over molecular self-assembly is reported. This strategy uses the reversible trans-cis photoisomerization of a novel azobenzene system, where the trans- and cis-forms self-assemble into dramatically different higher-order structures. The trans-azobenzene form of this molecule associates into infinite hydrogen-bonded linear tapes, while the cis-azobenzene form undergoes hydrogen-bonded self-assembly into cyclic tetramers. This results in a second level of association, where the cis-hydrogen-bonded supramolecular cycles ultimately form long, rod-like aggregates through stacking interactions.