Nanocomposite hyaluronic acid-based hydrogel for the treatment of esophageal fistulas.

Fistulas are abnormal connections between two body parts that can impair the quality of life. The use of biological glues represents the least invasive procedure to fill the fistula; however, it is limited by the need of multiple injections, the persistence of infection and the failure in the treatment of high-output fistulas. We describe herein the use of an injectable nanocomposite hydrogel that is able to form in situ a tissue-mimicking matrix as an innovative material for the treatment of esophageal fistulas. Injectable hydrogels that have the dual advantage of being implantable with a minimally invasive approach and of adapting their shape to the target cavity, while the introduction of mesoporous silica nanoparticles opens the possibility of drug/biomolecules delivery. The hydrogel is based on hyaluronic acid (HA), the crosslinking process occurs at physiological conditions leading to a hydrogel made of >96% by water and with a large-pore micro-architecture. The kinetic profile of the hydrogel formation is studied as a function of HA molecular weight and concentration with the aim of designing a material that is easily injectable with an endoscopic needle, is formed in a time compatible with the surgical procedure and has final mechanical properties suitable for cell proliferation. The in vivo experiments (porcine model) on esophageal-cutaneous fistulas, showed improved healing in the animals treated with the hydrogel compared with the control group.

Application of a novel material in the inguinal region using a totally percutaneous approach in an animal model: a new potential technique?

PURPOSE: To evaluate the feasibility and safety of a new percutaneous image-guided surgery technique to simulate a hernia repair using hydrogel. MATERIALS AND METHODS: A comparative prospective study was conducted in animals, with survival. Five pigs without any hernias were used. A hydrogel was injected at a site corresponding to the preperitoneal inguinal region. This procedure was performed bilaterally. An image-guided needle (ultrasound and computed tomography) was used, through which the material was injected. After survival, the local and systemic inflammatory reaction generated by the new material, was studied. RESULTS: All animals survived the procedure. No hemorrhagic or infectious complications were reported. The solidification of the material occurred as expected. In eight out of ten cases, the material was found in the planned site. No systemic inflammatory reaction secondary to the administration of hydrogel was reported. The adhesion of the material to surrounding tissues was satisfactory. CONCLUSION: The introduction of a liquid material which solidifies after injection in a short time (hydrogel) using a needle is feasible. The combined CT-scan and US image guidance allows for the percutaneous placement of the needle in the required location. The introduced hydrogel remains in this space, corresponding to the inguinal region, without moving. The placed hydrogel compresses the posterior wall composed of the transversalis fascia, supporting the potential use of hydrogel for hernia defects.

Stabilisation effects of phosphane ligands in the homogeneous approach of sunlight induced hydrogen production.

Most of the systems for photochemical hydrogen production are not stable and suffer from decomposition. With bis(bidentate) tetraphosphane ligands the stability increases enormously, up to more than 1000 h. This stability was achieved with a system containing osmium(ii) as a light harvesting antenna and palladium(ii) as a water reduction catalyst connected with a bis(bidentate) phosphane ligand in one molecule with the chemical formula [Os(bpy)2(dppcb)Pd(dppm)](PF6)4. With the help of electrochemical measurements as well as photophysical data and its single crystal X-ray structure, the electron transfer between the two active metal centres (light harvesting antenna, water reduction catalyst) was analysed. The distance between the two active metal centres was determined to be 7.396(1) Å. In a noble metal free combination of a copper based photosensitiser and a cobalt diimine-dioxime complex as water reduction catalyst a further stabilisation effect by the phosphane ligands is observed. With the help of triethylamine as a sacrificial donor in the presence of different monophosphane ligands it was possible to produce hydrogen with a turnover number of 1176. This completely novel combination is also able to produce hydrogen in a wide pH-range from pH = 7.0 to 12.5 with the maximum production at pH = 11.0. The influence of monophosphane ligands with different Tolman cone angles was investigated. Monophosphane ligands with a large Tolman cone angle (>160°) could not stabilise the intermediate of the cobalt based water reduction catalyst and so the turnover number is lower than for systems with an addition of monophosphane ligands with a Tolman cone angle smaller than 160°. The role of the monophosphane ligand during sunlight-induced hydrogen production was analysed and these results were confirmed with DFT calculations. Furthermore the crystal structures of two important Co(i) intermediates, which are the catalytic active species during the catalytic pathway, were obtained. The exchange of PPh3 with other tertiary phosphane ligands can have a major impact on the activity, depending on the coordination properties. By an exchange of monophosphane ligands with functionalised phosphane ligands (hybrid ligands) the hydrogen production was raised 2.17 times.

Unusual stability of dyads during photochemical hydrogen production.

Dyads for photochemical water splitting often suffer from instability during irradiation with visible light. However, the use of bis(bidentate) phosphines forming a five-membered ring enhances their stability. The coordination of these phosphor based chelates to soft metals like Pd(ii) prolongs the photocatalytic activity to 1000 hours. To avoid contribution to hydrogen production by colloidal metal, a small amount of Hg is added to the reaction mixture. In the course of our investigations, it turned out that colloidal palladium was not able to produce hydrogen under our irradiation conditions. As soon as metallic palladium emerged in our reaction vessels, no further hydrogen production was detected. This is confirmed by the observation that the hydrogen production depends on the kind of ancillary ligands present in the dyads. The first dyads of the type [MI(bpy)2(dppcb)MII(bpy)](4+) are presented (MI = Os, MII = Pd (1); MI = Ru, MII = Pd (2); MI = Os, MII = Pt (3); MI = Ru, MII = Pt (4)). In [Os(bpy)2(dppcb)Pd(dppm)](PF6)4 (5) the ancillary ligand is varied. Furthermore, it is also possible to produce hydrogen in an intermolecular way. Using different bidentate diphosphines instead of a bis(bidentate) tetraphosphine leads to this intermolecular approach, where the chromophore and the water reduction catalyst (WRC) belong now to two molecules. In this case the TON is sensitive to the type of diphosphine, which is only possible if intact molecules act as catalysts and no free palladium(0) is formed.

Ultrahigh magnetoresistance at room temperature in molecular wires.

Systems featuring large magnetoresistance (MR) at room temperature and in small magnetic fields are attractive owing to their potential for applications in magnetic field sensing and data storage. Usually, the magnetic properties of materials are exploited to achieve large MR effects. Here, we report on an exceptionally large (>2000%), room-temperature, small-field (a few millitesla) MR effect in one-dimensional, nonmagnetic systems formed by molecular wires embedded in a zeolite host crystal. This ultrahigh MR effect is ascribed to spin blockade in one-dimensional electron transport. Its generic nature offers very good perspectives to exploit the effect in a wide range of low-dimensional systems.

Dendrimer-modified solid supports: nanostructured materials with potential drug allergy diagnostic applications.

Complex functional materials consisting of bioactive molecules immobilized on solid supports present potential applications in biosensoring. Advances in the fabrication of these surface materials are of growing interest for antibody-based diagnosis. This work exploits dendrimers as versatile nanostructures for templating sensor surfaces and the critical role of the immobilization protocol in the solid supports cellulose and zeolites, of organic and inorganic composition respectively. The fabrication and characterization, including the degree of functionalization and reproducibility, of different nanostructured materials are described. To validate the approach, the fabricated supports were further used as a solid phase for developing a radioimmunoassay to detect immunoglobulin E (IgE) specific to penicillin, the antibody involved in immediate allergy responses to this drug. The dendrimer-modified supports provide assays with significantly enhanced sensitivity, as well as increase the availability of biomolecules for specific interaction and minimize nonspecific adsorptions through appropriate functionalization protocols in each case. The manufacturing methodology involved the use of a long, flexible hydrophilic spacer in the cellulose materials, and a higher surface density of the immobilized dendrimers in the zeolite crystals. The ability of hybrid zeolite materials in such biosensing applications was evaluated for the first time. The assays were validated in human serum samples from patients allergic to penicillin and from non-allergic controls. The specificity and improved sensitivity of the dendrimer- modified supports make these strategies versatile for different bioactive molecules and could have significant implications for the quantification of a wide range of specific IgE antibodies and other biomolecules of diagnostic interest.

Electroluminescent device with reversible switching between red and green emission.

Research on new materials for organic electroluminescence has recently focused strongly on phosphorescent emitters, with the aim of increasing the emission efficiency and stability. Here we report the fabrication of a simple electroluminescent device, based on a semiconducting polymer combined with a phosphorescent complex, that shows fully reversible voltage-dependent switching between green and red light emission. The active material is made of a polyphenylenevinylene (PPV) derivative molecularly doped with a homogeneously dispersed dinuclear ruthenium complex, which fulfils the dual roles of triplet emitter and electron transfer mediator. At forward bias (+4 V), the excited state of the ruthenium compound is populated, and the characteristic red emission of the complex is observed. On reversing the bias (-4 V), the lowest excited singlet state of the polymer host is populated, with subsequent emission of green light. The mechanism for the formation of the excited state of the PPV derivative involves the ruthenium dinuclear complex in a stepwise electron transfer process that finally leads to efficient charge recombination reaction on the polymer.

Metallocyclodextrins as building blocks in noncovalent assemblies of photoactive units for the study of photoinduced intercomponent processes.

Cyclodextrin cups have been employed to build supramolecular systems consisting of metal and organic photoactive/redox-active components; the photoinduced communication between redox-active units assembled in water via noncovalent interactions is established. The functionalization of a beta-cyclodextrin with a terpyridine unit, ttp-beta-CD, is achieved by protection of all but one of the hydroxyl groups by methylation and attachment of the ttp unit on the free primary hydroxyl group. The metalloreceptors [(beta-CD-ttp)Ru(ttp)][PF(6)](2), [(beta-CD-ttp)Ru(tpy)][PF(6)](2), and [Ru(beta-CD-ttp)(2)][PF(6)](2) are synthesized and fully characterized. The [(beta-CD-ttp)Ru(ttp)][PF(6)](2) metalloreceptor exhibits luminescence in water, centered at 640 nm, from the (3)MLCT state with a lifetime of 1.9 ns and a quantum yield of Phi = 4.1 x 10(-)(5). Addition of redox-active quinone guests AQS, AQC, and BQ to an aqueous solution of [(beta-CD-ttp)Ru(ttp)](2+) results in quenching of the luminescence up to 40%, 20%, and 25%, respectively. Measurement of the binding strength indicates that, in saturation conditions, 85% for AQS and 77% for AQC are bound. The luminescence quenching is attributed to an intercomponent electron transfer from the appended ruthenium center to the quinone guest inside the cavity. Control experiments demonstrate no bimolecular quenching at these conditions. A photoactive osmium metalloguest, [Os(biptpy)(tpy)][PF(6)], is designed with a biphenyl hydrophobic tail for insertion in the cyclodextrin cavity. The complex is luminescent at room temperature with an emission band maximum at 730 nm and a lifetime of 116 ns. The osmium(III) species are formed for the study of photoinduced electron transfer upon their assembly with the ruthenium cyclodextrin, [(beta-CD-ttp)Ru(ttp)](2+). Time-resolved spectroscopy studies show a short component of 10 ps, attributed to electron transfer from Ru(II) to Os(III) giving an electron transfer rate 9.5 x 10(9) s(-)(1).