Banana-shaped molecules peculiarly oriented in a magnetic field: (2)H NMR spectroscopy and quantum mechanical calculations.

The orientational properties of the banana-shaped liquid crystal 4-chloro-1,3-phenylenebis{4-[4'-(10-undecenyloxy)]benzoyloxy} benzoate (ClPbis11BB) are reported in the nematic phase under the effect of an external magnetic field. A new hypothesis, which states that the central ring of the aromatic core is oriented perpendicularly to the external magnetic field, is proposed. In support of this hypothesis, a series of studies based on (2)H NMR spectroscopy, both in the bulk and in solution, are discussed. (2)H NMR measurements on three selectively deuterium-labelled isotopomers are presented, together with DFT results from B3LYP/cc-pvDz calculations performed on the aromatic core. The rather flat shape of the investigated intramolecular energy surface allows for several different conformations to be populated, the computed magnetic susceptibilities of which are consistent with the proposed hypothesis of peculiar orientation of banana-shaped molecules. Moreover, the orientation of the magnetic susceptibility tensor is shown to be strongly dependent on the internal conformation of the banana-shaped molecules.     

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.     

A countable class of non-homeomorphic homology spheres with Heegaard genus two

We construct a countable set of prime non-homeomorphic homology spheres with Heegaard genus 2.

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Sunto Si prova l'esistenza di una classe numerabile di sfere omologiche prime non omeomorfe con genere di Heegaard 2.

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Work performed under the auspicies of the G.N.S.A.G.A. of the C.N.R. (National Research Council of Italy) and within the project Geometria delle Varietà Differenziabili of the M.P.I. (Italy).     

An Asymmetric Edge-Sharing Bioctahedral Complex: (η2-DAniF)MoIII(μ-DAniF)2(μ-O,Cl)MoVCl2 (DAniF=N,N′-di-p-anisylformamidinate)

A novel asymmetric, edge-sharing bioctahedral complex with formamidinato ligands ( ²-DAniF)Mo(-DAniF)₂(-O,Cl)MoCl₂, 1, (DAniF=N,N-di-p-anisylformamidinate) has been isolated as a byproduct from the preparation of the dimolybdenum(II,III) compound Mo₂(DAniF)₃Cl₂. An X-ray crystallographic study shows that the structure consists of edge-sharing bioctahedra, with the shared edge defined by the vector joining the: -O and -Cl ligands. Compound 1 is best formulated as a mixed-valent Mo^IIIMo^V compound, the Mo(V) ion being that with the two terminal Cl^– ligands. The cyclic voltammogram of 1 shows a reversible reduction at –0.472 V and a reversible oxidation at 1.028 V vs. the Ag/AgCl reference electrode, while the absorption spectrum of 1 reveals an intense low energy absorption at 523 nm ( _max=12 500) which is attributed to an intervalence charge transfer transition. Crystallographic data for 1 are as follows: a=13.387(1) Å, b=15.500(2) Å, c=21.855(2) Å, =98.786(2)°, V=4481.8(8) ų, P2₁/c, R1 (wR2)=0.082 (0.177).     

Synthetic erythropoietic proteins: tuning biological performance by site-specific polymer attachment

Chemical synthesis in combination with precision polymer modification allows the systematic exploration of the effect of protein properties, such as charge and hydrodynamic radius, on potency using defined, homogeneous conjugates. A series of polymer-modified synthetic erythropoiesis proteins were constructed that had a polypeptide chain similar to the amino acid sequence of human erythropoietin but differed significantly in the number and type of attached polymers. The analogs differed in charge from +5 to -26 at neutral pH and varied in molecular weight from 30 to 54 kDa. All were active in an in vitro cell proliferation assay. However, in vivo potency was found to be strongly dependent on overall charge and size. The trends observed in this study may serve as starting points for the construction of more potent synthetic EPO analogs in the future.     

Effect of time on the interfacial and foaming properties of beta-lactoglobulin/acacia gum electrostatic complexes and coacervates at pH 4.2

The electrostatic complexation between beta-lactoglobulin and acacia gum was investigated at pH 4.2 and 25 degrees C. The binding isotherm revealed a spontaneous exothermic reaction, leading to a DeltaHobs = -2108 kJ mol(-1) and a saturation protein to polysaccharide weight mixing ratio of 2:1. Soluble electrostatic complexes formed in these conditions were characterized by a hydrodynamic diameter of 119 +/- 0.6 nm and a polydispersity index of 0.097. The effect of time on the interfacial and foaming properties of these soluble complexes was investigated at a concentration of 0.1 wt % at two different times after mixing (4 min, referred as t approximately 0 h and t = 24 h). At t approximately 0 h, the mixture is mainly made of aggregating soluble electrostatic complexes, whereas after 24 h these complexes have already insolubilize to form liquid coacervates. The surface elasticity, viscosity and phase angle obtained at low frequency (0.01 Hz) using oscillating bubble tensiometry revealed higher fluidity and less rigidity in the film formed at t approximately 0 h. This observation was confirmed by diminishing bubble experiments coupled with microscopy of the thin film. It was thicker, more homogeneous and contained more water at t approximately 0 h as compared to t = 24 h (thinner film, less water). This led to very different gas permeability's of Kt approximately 0 h = 0.021 cm s(-1) and Kt=24 h) = 0.449 cm s(-1), respectively. Aqueous foams produced with the beta-lactoglobulin/acacia gum electrostatic complexes or coacervates exhibited very different stability. The former (t approximately 0 h) had a stable volume, combining low drainage rate and mainly air bubble disproportionation as the destabilization mechanism. By contrast, using coacervates aged for 24 h, the foam was significantly less stable, combining fast liquid drainage and air bubble destabilization though fast gas diffusion followed by film rupture and bubble coalescence. The strong effect of time on the air/water interfacial properties of the beta-lactoglobulin/acacia gum electrostatic complexes can be understood by their reorganization at the interface to form a coacervate phase that is more fluid/viscous at t approximately 0 h vs rigid/elastic at t = 24 h.     

Synthesis of [1,3]dithiole and spiro[1,3]dithiole thiopyran derivatives of the [1,2]dithiolo[1,4]thiazine ring system

We report the synthesis of some new polysulfur-nitrogen heterocycles by cycloaddition reactions to readily available tricyclic condensed 1,2-dithiole-3-thiones. Thus, treatment of bis[1,2]dithiolopyrrole ketothione 1 with diacyl acetylenes gave the bis-aducts 2a-d. On the other hand, cycloaddition of bis[1,2]dithiolo[1,4]thiazine ketothione 3 with 1 equiv of acyl or diacyl acetylenes gave [1,3]dithiolylidenyl[1,2]dithiolo[1,4]thiazines 4a-f in fair to high yields. Catalysis by scandium triflate was used in the reactions that implied the less reactive dipolarophiles. Treatment of 3 with 2 equiv of DBA gave the bis-aduct 5a, and reaction of 4c with DMAD gave the mixed bis-adduct 5b. Cyclic voltammetry of selected examples showed irreversible processes that were influenced by the electrochemical activity of peripheral groups bonded to the heterocyclic system.