Synthesis and spectral investigation of Al(III) catechin/beta-cyclodextrin and Al(III) quercetin/beta-cyclodextrin inclusion compounds

Al-catechin/beta-cyclodextrin and Al-quercetin/beta-cyclodextrin (beta-CD) inclusion compounds were synthesized and characterized by IR, UV-vis, H-1 and C-13 NMR and TG and DTA analyses. Because quercetin is sparingly soluble in water, the stability constants of the Al-quercetin/beta-CD and Al-catechin/beta-CD compounds were determined by phase solubility studies. The A(L)-type diagrams indicated the formation of 1:1 inclusion compounds and allowed calculation of the stability constants. The thermodynamic parameters were obtained from the dependence of the stability constants on temperature and results indicated that the formation of the inclusion compounds is an enthalpically driven process. The thermal decomposition of the solid Al-quercetin/beta-CD and Al-catcchin/beta-CD inclusion compounds took place at different stages, compared with the respective precursors, proving that an inclusion complexation process really occurred. (C) 2007 Published by Elsevier B.V.

The in vitro antioxidant properties of the Al-quercetin/beta CD and Al-catechin/beta CD inclusion compounds, rationalized in terms of their electrochemical behaviour

Inclusion compounds of Al-quercetin and Al-catechin complexes with beta-cyclodextrin (beta CD) were investigated. The complex and the inclusion compound of quercetin are more effective DPPHaEuro cent scavengers than the corresponding catechin compounds and the inclusion does not compromise their scavenging abilities, with only a slight decrease in the EC50 values. This is in accordance with the electrochemical data, which revealed that the inclusion compounds have lower diffusion coefficients in aqueous solution than the non-included compounds. For the quercetin compounds, some spectroscopic properties were also addressed by means of UV-visible and NMR measurements in aqueous media.

Triangular ruthenium acetate clusters containing the bis(pyridyl)propane ligand and their inclusion chemistry with beta-cyclodextrin

The triruthenium carboxylate cluster [Ru(3)O(OAc)(6)(py)(2)(bpp)](+) (OAc = acetate) containing the bridging 1,3-bis(4-pyridyl)propane (bpp) ligand, and its dimeric species [{Ru(3)O(OAc)(6)(py(2))}(2)(mu-bpp)](2+) were synthesized in order to investigate their inclusion compounds with beta-cyclodextrin (beta-CD). Characterization of the complexes was carried out based on spectroscopic, electrochemical and spectroelectrochemical techniques, while the formation of inclusion complexes was evaluated using (1)H NMR/NOESY spectroscopy. Since bpp is a flexible ligand, a DFT study was carried out in order to characterize its conformational isomers and their possible role in the host-guest chemistry with beta-CD. Instead of observing the formation of inclusion compounds with different stoichiometries, we observed the formation of 1:1 bpp/beta-CD compounds in which the bpp ligand assumes different conformations. The assembly of polymetallic rotaxane species was successfully demonstrated by monitoring the (1)H NMR spectra of the monomeric cluster species in the presence of aquapentacyanoferrate(II) ions and beta-CD.

Desenvolvimento de Têxteis com Capacidade de Libertação de Agentes Funcionais

Mestrado em Engenharia Química - Ramo Tecnologias de Protecção Ambiental

Cucurbiturilas

This review article describes the properties and the main applications of the glicol[n]urils. These compounds are cavitands made of n glycolurilic units arranged in circles, giving rise to extremely symmetric toroidal molecules. The cucurbit[n]urils create this way variable-sized hydrophobic cavities and the glycolurilic carbonyles delimit two portals on these cavities, slightly narrower than their internal radii. Their structure, physical and chemical properties favor the formation of inclusion compounds, and turn them into important building blocks for supramolecular chemistry and nanotechnology.

Preparation of association compound between rhodium(II) citrate and β-cyclodextrin

Inclusion compound of rhodium(II) citrate with β-cyclodextrin in a 1:1 molar ratio was prepared using freeze-drying method. X-ray diffactometry, thermal analysis (TG/DTG/DSC), infrared and ¹H-NMR with ¹H spin lattice relaxation (¹H T1) measurements and 13C techniques were used to characterize the system prepared. The results indicated the formation of inclusion or association compounds between rhodium(II) citrate and β-cyclodextrin.

Ni/Pd@MIL-101: Synergistic Catalysis with Cavity-Conform Ni/Pd Nanoparticles

Deutsche Forschungsgemeinschaft [SFB 840]

A stochastic principle behind polar properties of condensed molecular matter

A statistical mechanics view leads to the conclusion that polar molecules allowed to populate a degree of freedom for orientational disorder in a condensed phase thermalize into a bi-polar state featuring zero net polarity. In cases of orientational disorder polar order of condensed molecular matter can only exist in corresponding sectors of opposite average polarities. Channel type inclusion compounds, single component molecular crystals, solid solutions, optically anomalous crystals, inorganic ionic crystals, biomimetic crystals and biological tissues investigated by scanning pyroelectric and phase sensitive second harmonic generation microscopy all showed domains of opposite polarities in their final grown state. For reported polar molecular crystal structures it is assumed that kinetic hindrance along one direction of the polar axis is preventing the formation of a bi-polar state, thus allowing for a kinetically controlled mono-domain state. In this review we summarize theoretical and experimental findings leading to far reaching conclusions on the polar state of solid molecular matter. “… no stationary state … of a system has an electrical dipole moment.” P. W. Anderson, Science, 1972, 177, 393.

Lemon oil to beta-cyclodextrin ratio effect on the inclusion efficiency of beta-cyclodextrin and the retention of oil volatiles in the complex

Microencapsulation of lemon oil was undertaken with beta-cyclodextrin using a precipitation method at the five lemon oil to beta-cyclodextrin ratios of 3:97, 6:94, 9:91, 12:88, and 15:85 (w/w) in order to determine the effect of the ratio of lemon oil to beta-cyclodextrin on the inclusion efficiency of beta-cyclodextrin for encapsulating oil volatiles. The retention of lemon oil volatiles reached a maximum at the lemon oil to beta-cyclodextrin ratio of 6:94; however, the maximum inclusion capacity of beta-cyclodextrin and a maximum powder recovery were achieved at the ratio of 12:88, in which the beta-cyclodextrin complex contained 9.68% (w/w) lemon oil. The profile and proportion of selected flavor compounds in the beta-cyclodextrin complex and the starting lemon oil were not significantly different.

Phenolic compounds from olive mill wastes: Health effects, analytical approach and application as food antioxidants

Background Over the years, food industry wastes have been the focus of a growing interest due to their content in high added-value compounds. A good example are the olive oil by-products (OOBP), which retain a great amount of phenolic compounds during olive oil production. Their structure and biological properties justify their potential use as antioxidants in other food products. The efficient recovery of phenolic compounds has been extensively studied and optimized in order to maximize their reintroduction in the food chain and contribute to a higher valorization and better management of wastes from olive oil industry. Scope and approach This paper reviews the most representative phenolic compounds described in OOBP and their biological properties. New extraction procedures to efficiently recover these compounds and the most advanced chromatographic techniques that have been used for a better understanding of the phenolic profile of these complex matrices are also referred. Finally, this paper reports the main applications of OOBP, with emphasis on their phenolic content as natural antioxidants for food applications. Key findings and conclusions Besides their antioxidant activity, phenolic compounds from OOBP have also shown antimicrobial and antitumoral properties. Their application as food antioxidants requires new extraction techniques, including the use of non-toxic solvents and, in a pilot scale, the use of filters and adsorbent resins. The inclusion of phenolic compounds from OOBP in some food matrices have improved not only their antioxidant capacity but also their sensory attributes.

Thioflavin-S staining of bacterial inclusion bodies for the fast, simple, and inexpensive screening of amyloid aggregation inhibitors

Amyloid aggregation is linked to a large number of human disorders, from neurodegenerative diseases as Alzheimer"s disease (AD) or spongiform encephalopathies to non-neuropathic localized diseases as type II diabetes and cataracts. Because the formation of insoluble inclusion bodies (IBs) during recombinant protein production in bacteria has been recently shown to share mechanistic features with amyloid self-assembly, bacteria have emerged as a tool to study amyloid aggregation. Herein we present a fast, simple, inexpensive and quantitative method for the screening of potential anti-aggregating drugs. This method is based on monitoring the changes in the binding of thioflavin-S to intracellular IBs in intact Eschericchia coli cells in the presence of small chemical compounds. This in vivo technique fairly recapitulates previous in vitro data. Here we mainly use the Alzheimer"s related beta-amyloid peptide as a model system, but the technique can be easily implemented for screening inhibitors relevant for other conformational diseases simply by changing the recombinant amyloid protein target. Indeed, we show that this methodology can be also applied to the evaluation of inhibitors of the aggregation of tau protein, another amyloidogenic protein with a key role in AD.