Cyclocreatine, an anticancer and neuroprotective agent. Spectroscopic, structural and theoretical study

The structural, spectroscopic and theoretical study of cyclocreatine (1-carboxymethyl-2-iminoimidazolidine, CyCre) has been performed prompted by the biological relevance of the molecule and its potential role as a ligand in biometalic compounds. The crystal structure of CyCre has been determined by X-ray diffraction methods. The compound crystallizes as a zwitterion in the monoclinic system, space group P2(1)/c. The crystal is further stabilized by a network of N-H center dot center dot center dot O bonds. Infrared and Raman spectra of the solid, electronic spectra of aqueous solutions at different pH values and (1)H and (13)C NMR spectra have been recorded and analyzed. Band assignments were accomplished with the help of theoretical calculations. Optimized molecular geometries, harmonic vibrational frequencies and molecular electrostatic potentials were calculated using methods based on the density functional theory. (C) 2010 Elsevier B.V. All rights reserved.

Composition effects on ion transport in a polyelectrolyte gel with the addition of ion dissociators

The polymerization of lithium 2-acrylamido-2-methyl-1-propane sulphonic acid with N,N′-dimethylacrylamide has yielded polyelectrolyte gels which have the favourable property of being single ion conductors. The use of single ion conductors ensures that the transport number of lithium is close to unity. The mobility of the lithium ion is still quite low in these systems, resulting in low ionic conductivity. To increase ionic conductivity more charge carriers can be added however competing effects arise between increasing the number of charge carriers and decreasing the mobility of these charge carriers. In this paper the monomer ratio of the copolymer polyelectrolyte is varied to investigate the effect increasing the number of charge carriers has on the ionic conductivity and lithium ion and solvent diffusivity using pfg-NMR. Ion dissociators such as TiO₂ nano-particles and a zwitterionic compound based on 1-butylimidazolium-3-(N-butanesulfonate) have been added in an attempt to further increase the ionic conductivity of the system. It was found that the system with the highest ionic conductivity had the lowest solvent mobility in the presence of zwitterion. Without zwitterion the mobility of the solvent appears to determine the maximum ionic conductivity achievable.

Effect of zwitterions on electrochemical properties of oligoether-based electrolytes

Solid polymer electrolytes show great potential in electrochemical devices. Poly(ethylene oxide) (PEO) has been studied as a matrix for solid polymer electrolytes because it has relatively high ionic conductivity. In order to investigate the effect of zwitterions on the electrochemical properties of poly(ethylene glycol) dimethyl ether (G5)/lithium bis(fluorosulfonyl) amide (LiFSA) electrolytes, a liquid zwitterion (ImZ2) was added to the G5-based electrolytes. In this study, G5, which is a small oligomer, was used as a model compound for PEO matrices. The thermal properties, ionic conductivity, and electrochemical stability of the electrolytes with ImZ2 were evaluated. The thermal stabilities of all the G5-based electrolytes with ImZ2 were above 150 °C, and the ionic conductivity values were in the range of 0.8–3.0 mS cm−1 at room temperature. When the electrolytes contained less than 5.5 wt% ImZ2, the ionic conductivity values were almost the same as that of the electrolyte without ImZ2. The electrochemical properties were improved with the incorporation of ImZ2. The anodic limit of the electrolyte with 5.5 wt% ImZ2 was 5.3 V vs. Li/Li+, which was over 1 V higher than that of G5/LiFSA.

Structure of arginine overlayers at the aqueous gold interface: implications for nanoparticle assembly.

Adsorption of small biomolecules onto the surface of nanoparticles offers a novel route to generation of nanoparticle assemblies with predictable architectures. Previously, ligand-exchange experiments on citrate-capped gold nanoparticles with the amino acid arginine were reported to support linear nanoparticle assemblies. Here, we use a combination of atomistic modeling with experimental characterization to explore aspects of the assembly hypothesis for these systems. Using molecular simulation, we probe the structural and energetic characteristics of arginine overlayers on the Au(111) surface under aqueous conditions at both low- and high-coverage regimes. In the low-density regime, the arginines lie flat on the surface. At constant composition, these overlayers are found to be lower in energy than the densely packed films, although the latter case appears kinetically stable when arginine is adsorbed via the zwitterion group, exposing the charged guanidinium group to the solvent. Our findings suggest that zwitterion-zwitterion hydrogen bonding at the gold surface and minimization of the electrostatic repulsion between adjacent guanidinium groups play key roles in determining arginine overlayer stability at the aqueous gold interface. Ligand-exchange experiments of citrate-capped gold nanoparticles with arginine derivatives agmatine and N-methyl-l-arginine reveal that modification at the guanidinium group significantly diminishes the propensity for linear assembly of the nanoparticles.

Improvement of charge/discharge properties of oligoether electrolytes by zwitterions with an attached cyano group for use in lithium-ion secondary batteries

Zwitterions with a cyano group on the side chain (CZ) were synthesized. Although the addition of CZ caused a slightly negative effect on viscosity, ionic conductivity, limiting current density, and lithium transference number, the oxidation limit of PEGDME/lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) composites was improved to over 5 V. For charge/discharge testing using Li|electrolyte|LiCoO2 cells, the cycle stability of PEGDME/LiTFSA with CZ in the voltage range of 3.0-4.6 V was much higher than that of PEGDME/LiTFSA. Incorporating a small mole fraction of CZ into PEGDME-based electrolytes prevented an increase in the interface resistance between the electrolyte and cathode with increasing numbers of the cycle.

Langmuir films of an amide extracted from Piperaceae and its interaction with phospholipids

In this work, we investigate Langmuir monolayers froth an amide extracted from dried roots of Ottonia propinqua, a native Brazilian plant believed to exhibit anesthetic and hallucinogen activities. In addition to producing monolayers from the amide itself, we probe the molecular-level action of the amide on phospholipids employed as simple membrane models. The surface pressure-molecular area (pi-A) isotherms for the amide were little affected by a number of subphase conditions. Almost no changes were observed upon varying the compression speed, spreading volume onto the surface, ions in the subphase, ionic strength and the solution solvent. However, stronger effects occurred when the subphase temperature and pH were altered, as the isotherms were shifted to larger areas with increasing temperatures and decreasing pHs. These results are discussed in terms of the molecular packing adopted by the amide at the air-water interface. In the mixed films with arachidic acid, the area per molecule varied linearly with the concentration of amide, probably due to phase separation. on the other hand, in the mixed films with dipalmitoyl phosphatidyl choline (DPPC), small amounts of the amide were sufficient to change the pi-A isotherms significantly. This points to a strong molecular-level interaction, probably between the phosphate group in the zwitterion of DPPC and the nitrogen from the amidic group. (c) 2004 Elsevier B.V. All rights reserved.

Candida albicans adherence to an acrylic resin modified by experimental photopolymerised coatings: An in vitro study

Purpose: This study evaluated whether photopolymerised coatings containing zwitterion or hydrophilic monomers would reduce the adhesion of Candida albicans to an acrylic resin. Materials and methods: Disc-shaped samples (n = 468) were fabricated with rough or smooth surfaces. The samples did not receive any surface treatment (control) or were coated with one of the following experimental coatings (2-hydroxyethyl methacrylate - HE; 3-hydroxypropyl methacrylate - HP; and 2-trimethylammonium ethyl methacrylate chloride - T; and sulfobetaine methacrylate - S). The concentrations of the constituent monomers were 25, 30 or 35%. The water contact angles of the samples were measured, and half of the samples were exposed to saliva. The adherent yeast cells were counted after crystal violet staining. Results: For the smooth samples, the groups S35, HP35 and HE35 showed significantly lower number of adhered Candida than control, in the absence of saliva. There were no significant differences among the experimental and control groups for the rough samples, but the saliva decreased the cell numbers for groups S25, S30 and HP30. The photoelectron spectroscopy analysis confirmed the changes in the chemical compositions of the experimental samples. Conclusions: The experimental photopolymerised coatings changed the chemical composition and decreased C. albicans adhesion in the groups S35, HP35 and HE35, suggesting that they should be further investigated. © 2012 The Gerodontology Society and John Wiley & Sons A/S.

Efetividade de vernizes fotopolimerizáveis experimentais na redução da hidrofobicidade e adesão de Candida albicans em uma resina para base de prótese

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

In vitro evaluation of adherence of Candida albicans, Candida glabrata, and Streptococcus mutans to an acrylic resin modified by experimental coatings

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

Protonation Pattern, Tautomerism, Conformerism, and Physicochemical Analysis in New Crystal Forms of the Antibiotic Doxycycline

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Novel Synthesis of Carbocycles and Heterocycles Employing Zwitterions Derived from Allenic Esters

Carbon-carbon and carbon-heteroatom bond formations constitute the central events in organic synthesis. In view of this, much of the research in organic synthesis has been focused on devising novel and efficient methods for such bond constructions. In general, polar, pericyclic and radical methodologies are employed for this purpose. The polar and radical reactions proceed via reactive intermediates such as carbanions, enols/enolates, enamines, carbocations, radical cations, radical anions, carbenes, zwitterions etc. In recent years, there has been enormous interest in the chemistry of zwitterionic species largely from the standpoint of their applications in multicomponent reactions (MCRs) and organocatalytic reactions. Zwitterions formed by the addition of nucleophiles to electrophilic π-systems such as acetylenic esters and azoesters have been the subject of extensive investigations; their synthetic utility, however, remained largely unexplored. Investigations in a number of laboratories, including our own, have shown that zwitterions of the type mentioned above on reaction with electrophiles give rise to carbo- and heterocyclic products by 1,3- or 1,4-dipolar cycloadditions. Recently, allenoates, another class of active π-systems were introduced to this field. Against this background, a systematic investigation of the reactions of various zwitterions derived from allenoates with different electrophiles especially 1,2-diones, were carried out. The results of these studies are embodied in the thesis entitled “Novel Synthesis of Carbocycles and Heterocycles Employing Zwitterions Derived from Allenic Esters”.