Polyelectrolyte multilayers and degradable polymer layers as multicompartment films

Polyelectrolyte multilayers are now a well established concept with numerous potential applications in particular as biomaterial coatings. To timely control the biological activity of cells in contact with a substrate, multicompartment films made of different polyelectrolyte multilayers deposited sequentially on the solid substrate constitute a promising new approach. In a first paper (Langmuir 2004, 20, 7298) we showed that such multicompartment films can be designed by alternating exponentially growing polyelectrolyte multilayers acting as reservoirs and linearly growing ones acting as barriers. In the present study, we first demonstrate however that these barriers composed of synthetic polyelectrolytes are not degraded despite the presence of phagocytic cells. We propose an alternative approach where exponentially growing poly(L-lysine)/hyaluronic acid (PLL/HA) multilayers, used as reservoirs, are alternated with biodegradable polymer layers consisting in poly(lactic-co-glycolic acid) (PLGA) and acting as barriers for PLL chains that diffuse within the PLL/HA reservoirs. We first show that these PLGA layers can be deposited alternatively with PLL/HA multilayers leading to polyelectrolyte multilayer/hydrolyzable polymeric layer films and acting as a reservoirs/barriers system. Bone marrow cells seeded on these films ending by a PLL/HA reservoir rapidly degrade it and internalize the PLL chains confined in this reservoir. Then the cells degraded locally the PLGA barrier and internalize the PLL localized in a lower (PLL/HA) compartment after 5 days of seeding. By changing the thickness of the PLGA layer, we hope to be able to tune the time delay of degradation. Such mixed architectures made of polyelectrolyte multilayers and hydrolyzable polymeric layers could act as coatings allowing us to induce a time scheduled cascade of biological activities. We are currently working on the use of comparable films with compartments filled by proteins or peptides and in which the degradation of the barriers results from a hydrolysis over tunable time scales.     

Triplet state properties of the benzo[α]pyrene-DNA complex as determined by optically detected zero-field magnetic resonance

The zero-field transitions in the photoexcited triplet state of benzo[α]pyrene bound to DNA have been observed by optical detection of magnetic resonance of 2 K. The transition frequencies individual spin sublevel intersystem crossing rates were measured by monitoring the microwave-induced intensity changes of the triplettriplet absorption at 465.8 nm. The triplet state zero-field splitting and dynamics for the benzo[α]pyrene DNA complex are compared with these properties measured for benzo(α)pyrene in other solvent systems.     

Layer by layer buildup of polysaccharide films: physical chemistry and cellular adhesion aspects

The formation ofpolysaccharide films based on the alternate deposition of chitosan (CHI) and hyaluronan (HA) was investigated by several techniques. The multilayer buildup takes place in two stages: during the first stage, the surface is covered by isolated islets that grow and coalesce as the construction goes on. After several deposition steps, a continuous film is formed and the second stage of the buildup process takes place. The whole process is characterized by an exponential increase of the mass and thickness of the film with the number of deposition steps. This exponential growth mechanism is related to the ability of the polycation to diffuse "in" and "out" of the whole film at each deposition step. Using confocal laser microscopy and fluorescently labeled CHI, we show that such a diffusion behavior, already observed with poly(L-lysine) as a polycation, is also found with CHI, a polycation presenting a large persistence length. We also analyze the effect of the molecular weight (MW) of the diffusing polyelectrolyte (CHI) on the buildup process and observe a faster growth for low MW chitosan. The influence of the salt concentration during buildup is also investigated. Whereas the CHI/HA films grow rapidly at high salt concentration (0.15 M NaCl) with the formation of a uniform film after only a few deposition steps, it is very difficult to build the film at 10(-4) M NaCl. In this latter case, the deposited mass increases linearly with the number of deposition steps and the first deposition stage, where the surface is covered by islets, lasts at least up to 50 bilayer deposition steps. However, even at these low salt concentrations and in the islet configuration, CHI chains seem to diffuse in and out of the CHI/HA complexes. The linear mass increase of the film with the number of deposition steps despite the CHI diffusion is explained by a partial redissolution of the CHI/HA complexes forming the film during different steps of the buildup process. Finally, the uniform films built at high salt concentrations were also found to be chondrocyte resistant and, more interestingly, bacterial resistant. Therefore, the (CHI/HA) films may be used as an antimicrobial coating.     

Novel "Potentially antiaromatic", acidichromic quinonediimines with tunable delocalization of their 6 pi-electron subunits

We present a novel family of "potentially antiaromatic" alkyl-substituted p-benzoquinonediimine pH-dependent chromophores. It appears from the structural data that these overall 12 pi-electron molecules should be better considered as constituted by two chemically connected but electronically not conjugated 6 pi-electron subunits. Molecule 5 appears to be the first example of two separated, conjugated, and localized 6 pi-electron systems that can be tuned by reversible protonation to become delocalized. The mono- and diprotonated derivatives have been characterized by spectroscopic methods and X-ray diffraction. These systems develop supramolecular interactions in the solid state that clearly reflect the degree of protonation and depend on the nature of the counterion. These compounds constitute new chromophores for which the color can be tuned depending on the degree of protonation, going in solution from yellow for 5 to red for 5.HCl and blue for 5.2HCl. Theoretical calculations have provided a deeper insight into the electronic structure of these molecules and allowed an assignment of the experimental UV-vis spectra. The visible and near-UV spectrum of the neutral and protonated benzoquinonediimines can be classically assigned from the coupling of two 6 pi-electron polymethine units. TD-DFT calculations confirm the observed red shift of the two lowest pi --> pi* transitions of the benzoquinonediimines upon protonation and relate it to the moderate energy lowering of the HOMO --> LUMO transition induced by the delocalization of the polymethine pi system.     

Revised analysis of the structure of the v1 band of methane

The CARS spectrum of the v₁ band of ₁₂CH₄ at a pressure of 14 mbar was recorded using cw excitation in the cavity of a ring argon ion laser. The analysis of the intensity profile of the obarred spectrum led to the detection of inconsistencies with the hitherto proposed calculated positions of transitions with J = 7 to J = 10 and to a relocation of the corresponding lines.     

A dinuclear uranium(IV) complex of the chelating ligand 1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­diene

The ligand 1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­diene (cp*py) forms a dinuclear complex with U^IV, i.e. di‐μ‐oxo‐bis­{chloro­(diethyl ether‐κO)[(η⁵,κN)‐1,2,3,4‐tetra­methyl‐5‐(2‐pyridyl)­cyclo­penta­dienyl]uranium(IV)}, [U₂Cl₂O₂(C₁₄H₁₆N)₂(C₄H₁₀O)₂], in which cp*py acts as a chelating ligand, being bound to the metal atom by the cyclo­penta­dienyl unit and also by the N atom of the pyridyl ring.     

The fragmentation of 1-phenyl-2-propen-1-ol under electron impact

The electron impact mass spectra of 1-phenyl-2-propen-1-ol and its specifically deuterated analogues have been investigated. Most of the decomposition pathways involve skeletal rearrangements or hydrogen atom transfers, such that a rearrangement of the excited molecular ions of 1-phenyl-2-propen-1-ol to molecular ions of cinnamic alcohol and/or cinnamaldehyde can be anticipated.     

Probing the glycosidic linkage: UV and IR ion-dip spectroscopy of a lactoside

The beta(1-->4) glycosidic linkage found in lactose is a prevalent structural motif in many carbohydrates and glycoconjugates. Using UV and IR ion-dip spectroscopies to probe benzyl lactoside isolated in the gas phase, we find that the disaccharide unit adopts only a single, rigid structure. Its fully resolved infrared ion-dip spectrum is in excellent agreement with that of the global minimum structure computed ab initio. This has glycosidic torsion angles of phi(H) (H1-C1-O-C4') approximately 180 degrees and psi(H) (C1-O-C4'-H4') approximately 0 degrees which correspond to a rotation of approximately 150 degrees about the glycosidic bond compared to the accepted solution-phase conformation. We discuss the biological implications of this discovery and the generality of the strategies employed in making it.     

Radical Cation States of 2,3,5,6,7,8-Hexamethylidenebicyclo [2.2.2]octane

The photoelectron spectrum of the title compound is reported and assigned by correlation with the photoelectron spectra of related molecules.     

Stereochimie de la deprotonation et de la reaction d'aldolisation des dithioesters

Cis lithium thioenolates are preferentially formed by deprotonation of dithiopropanoates with lithium diisopropylamide in tetrahydro-furan at -78°C. The cis selectivity observed, is unproved by increasing the alkylthio group size or by the ability of this group to chelate the lithium cation. When more bulkier bases such as lithium 2,2,6,6-tetramethylpiperi-dide or lithium hexamethyldisilazane are used, the selectivity is lowered. This lowering of selectivity is suppressed when the deprotonation is performed in presence of 12-crown-4. Addition of hexamethyl phosphoramide to the base does not invert the selectivity as it uas reported for the deprotonation of esters ; a rather better cis selectivity is reached in the case of methoxymethyl dithiopropanoate. These original results are well understood in terms of an open transition state model. Preformed lithium thioenolates are reacted uith a variety of aldehydes and afford stereo-specifically syn aldols. The influence of hexamethylphosphoramide and reaction time is also examined.