Propriedades analíticas de materiais a base de sílica e óxido de titânio modificados

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A low molecular weight hydro and organogelator derived from an isohexide and sol-gel transcription of the alcogel

Heating 2,5-di-O-methanesulfonyl-1,4:3,6-dianhydro-D-sorbitol (1) in a range of solvents led to the formation of a gel state at low concentrations. 1 was found to gel aromatics, alcohols and water. The structure of 1 in the solid state was solved by single crystal X-ray crystallography; no strong hydrogen bonds or associated solvents were found in the crystal. Electron micrographs revealed the morphology of the gels to be predominantly rod-like. The ethanol alcogel was used to template silica by sol-gel transcription.

DNA block copolymers - synthesis, morphologies and applications

The last decades have witnessed significant and rapid progress in polymer chemistry and molecular biology. The invention of PCR and advances in automated solid phase synthesis of DNA have made this biological entity broadly available to all researchers across biological and chemical sciences. Thanks to the development of a variety of polymerization techniques, macromolecules can be synthesized with predetermined molecular weights and excellent structural control. In recent years these two exciting areas of research converged to generate a new type of nucleic acid hybrid material, consisting of oligodeoxynucleotides and organic polymers. By conjugating these two classes of materials, DNA block copolymers are generated exhibiting engineered material properties that cannot be realized with polymers or nucleic acids alone. Different synthetic strategies based on grafting onto routes in solution or on solid support were developed which afforded DNA block copolymers with hydrophilic, hydrophobic and thermoresponsive organic polymers in good yields. Beside the preparation of DNA block copolymers with a relative short DNA-segment, it was also demonstrated how these bioorganic polymers can be synthesized exhibiting large DNA blocks (>1000 bases) applying the polymerase chain reaction. Amphiphilic DNA block copolymers, which were synthesized fully automated in a DNA synthesizer, self-assemble into well-defined nanoparticles. Hybridization of spherical micelles with long DNA templates that encode several times the sequence of the micelle corona induced a transformation into rod-like micelles. The Watson-Crick motif aligned the hydrophobic polymer segments along the DNA double helix, which resulted in selective dimer formation. Even the length of the resulting nanostructures could be precisely adjusted by the number of nucleotides of the templates. In addition to changing the structural properties of DNA-b-PPO micelles, these materials were applied as 3D nanoscopic scaffolds for organic reactions. The DNA strands of the corona were organized by hydrophobic interactions of the organic polymer segments in such a fashion that several DNA-templated organic reactions proceeded in a sequence specific manner; either at the surface of the micelles or at the interface between the biological and the organic polymer blocks. The yields of reactions employing the micellar template were equivalent or better than existing template architectures. Aside from its physical properties and the morphologies achieved, an important requirement for a new biomaterial is its biocompatibility and interaction with living systems, i.e. human cells. The toxicity of the nanoparticles was analyzed by a cell proliferation assay. Motivated by the non-toxic nature of the amphiphilic DNA block copolymers, these nanoobjects were employed as drug delivery vehicles to target the anticancer drug to a tumor tissue. The micelles obtained from DNA block copolymers were easily functionalized with targeting units by hybridization. This facile route allowed studying the effect of the amount of targeting units on the targeting efficacy. By varying the site of functionalization, i.e. 5’ or 3’, the outcome of having the targeting unit at the periphery of the micelle or in the core of the micelle was studied. Additionally, these micelles were loaded with an anticancer drug, doxorubicin, and then applied to tumor cells. The viability of the cells was calculated in the presence and absence of targeting unit. It was demonstrated that the tumor cells bearing folate receptors showed a high mortality when the targeting unit was attached to the nanocarrier.

The effect of template phase on the structures of As-synthesized silica nanoparticles with fragile didodecyldimethylammonium bromide vesicles as templates

The effect of template phase on the structures of as-synthesized silica nanoparticles with fragile DDAB vesicles as templates is reported. It is found that the template phase plays a critical role in the growth process of silica: the unstable DDAB vesicles in liquid-crystalline phase often lead to the formation of mesostructured solid spheres, and the rather stable DDAB vesicles in gel phase lead to the formation of hollow spheres with less mesostructures.

Complex aggregates of silica microspheres by the use of a polymer template

Evaporation of a droplet of silica microsphere suspension on a polystyrene and poly(methyl methacrylate) blend film with isolated holes in its surface has been exploited as a means of particles self-assembly. During the retraction of the contact line of the droplet, spontaneous dewetting combined with the strong capillary force pack the silica microspheres into the holes in the polymer surface. Complex aggregates of colloids are formed after being exposed to acetone vapor. The morphology evolution of the underlying polymer film by exposure to acetone solvent vapor is responsible for the complex aggregates of colloids formation.

Structure and Function of Hemoglobin Confined Inside Silica Nanotubes

Investigations on the structure and function of hemoglobin (Hb) confined inside sol-gel template synthesized silica nanotubes (SNTs) have been discussed here. Immobilization of hemoglobin inside SNTs resulted in the enhancement of direct electron transfer during an electrochemical reaction. Extent of influence of nanoconfinement on protein activity is further probed via ligand binding and thermal stability studies. Electrochemical investigations show reversible binding of n-donor liquid ligands, such as pyridine and its derivatives, and predictive variation in their redox potentials suggests an absence of any adverse effect on the structure and function of Hb confined inside nanometer-sized channels of SNTs. Immobilization also resulted in enhanced thermal stability of Hb. The melting or denaturation temperature of Hb immobilized inside SNTs increase by approximately 4 degrees C as compared with that of free Hb in solution.

Two highly unsymmetrical tetradentate (N3O) Schiff base copper(II) complexes: Template synthesis, structural characterization, magnetic and computational studies

Two new copper(II) complexes, [Cu-2(L-1)(2)](ClO4)(2) (1) and [Cu(L-2)(ClO4)] (2), of the highly unsymmetrical tetradentate (N3O) Schiff base ligands HL1 and HL2 (where HL1 = N-(2-hydroxyacetophenone)-bis-3-aminopropylamine and HL2 = N-(salicyldehydine)-bis-3-aminopropylamine) have been synthesised using a template method. Their single crystal X-ray structures show that in complex 1 two independent copper(II) centers are doubly bridged through sphenoxo-O atoms (O1A and O1B) of the two ligands and each copper atom is five-coordinated with a distorted square pyramidal geometry. The asymmetric unit of complex 2 consists of two crystallographically independe N-(salicylidene) bis(aminopropyl)amine-copper(II) molecules, A and B, with similar square pyramidal geometries. Cryomagnetic susceptibility measurements (5-300 K) on complex 1 reveal a distinct antiferromagnetic interaction with J=-23.6 cm(-1), which is substantiated by a DFT calculation (J=-27.6 cm(-1)) using the B3LYP functional. Complex 1, immobilized over highly ordered hexagonal mesoporous silica, shows moderate catalytic activity for the epoxidation of cyclohexene and styrene in the presence of TBHP as an oxidant.

Ultrasound-Triggered Controlled Drug Delivery and Biosensing Using Silica Nanotubes

Silica nanotubes (SNTs) have been demonstrated here as a versatile host for controlled drug delivery and biosensing. The sol-gel template synthesized SNTs have a slow rate of drug release. Application of an external stimulus in the form of ultrasound to or chemical functionalization of synthesized SNT results in higher yield of drug release as well as yield of drug release varying linearly with time. In case of controlled drug delivery triggered by ultrasound, drug yield as function of time is found to be heavily dependent on the ultrasound impulse protocol. Impulses of shorter duration (similar to 0.5 min) and shorter time intervals between successive impulses resulted in higher drug yields. Confinement of hemoglobin (Hb) inside nanometer sized channels of SNT does not have any detrimental effect on the native protein structure and function. Observance of significant enhancement in direct electron transfer of Hb makes the SNTs also promising for application in biosensors.

No More HF: Teflon-Assisted Ultrafast Removal of Silica to Generate High-Surface-Area Mesostructured Carbon for Enhanced CO2 Capture and Supercapacitor Performance

An innovative technique to obtain high-surface-area mesostructured carbon (2545m(2)g(-1)) with significant microporosity uses Teflon as the silica template removal agent. This method not only shortens synthesis time by combining silica removal and carbonization in a single step, but also assists in ultrafast removal of the template (in 10min) with complete elimination of toxic HF usage. The obtained carbon material (JNC-1) displays excellent CO2 capture ability (ca. 26.2wt% at 0 degrees C under 0.88bar CO2 pressure), which is twice that of CMK-3 obtained by the HF etching method (13.0wt%). JNC-1 demonstrated higher H-2 adsorption capacity (2.8wt%) compared to CMK-3 (1.2wt%) at -196 degrees C under 1.0bar H-2 pressure. The bimodal pore architecture of JNC-1 led to superior supercapacitor performance, with a specific capacitance of 292Fg(-1) and 182Fg(-1) at a drain rate of 1Ag(-1) and 50Ag(-1), respectively, in 1m H2SO4 compared to CMK-3 and activated carbon.

No More HF: Teflon-Assisted Ultrafast Removal of Silica to Generate High-Surface-Area Mesostructured Carbon for Enhanced CO2 Capture and Supercapacitor Performance

An innovative technique to obtain high-surface-area mesostructured carbon (2545m(2)g(-1)) with significant microporosity uses Teflon as the silica template removal agent. This method not only shortens synthesis time by combining silica removal and carbonization in a single step, but also assists in ultrafast removal of the template (in 10min) with complete elimination of toxic HF usage. The obtained carbon material (JNC-1) displays excellent CO2 capture ability (ca. 26.2wt% at 0 degrees C under 0.88bar CO2 pressure), which is twice that of CMK-3 obtained by the HF etching method (13.0wt%). JNC-1 demonstrated higher H-2 adsorption capacity (2.8wt%) compared to CMK-3 (1.2wt%) at -196 degrees C under 1.0bar H-2 pressure. The bimodal pore architecture of JNC-1 led to superior supercapacitor performance, with a specific capacitance of 292Fg(-1) and 182Fg(-1) at a drain rate of 1Ag(-1) and 50Ag(-1), respectively, in 1m H2SO4 compared to CMK-3 and activated carbon.

Palladium within ionic liquid functionalized mesoporous silica SBA-15 and its catalytic application in room-temperature Suzuki coupling reaction

Initially, pore walls of mesoporous silica SBA-15 with template were modified with chlorotrimethylsilane. Then imidazolium salts were similarly incorporated covalently in the inner pore walls of mesoporous silica SBA-15 albeit without the template. Finally, palladium salts were introduced into the pore channels of the previously processed mesoporous silica via electrostatic interaction. The resulting palladium catalysts demonstrated exceptional activity for the room-temperature Suzuki Coupling reaction in aqueous-organic mixed solvents and good recycling ability for at least 4-6 times.