Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks

We report the self-assembly of a new family of hydrophobic,bis(pyridyl) PtII complexes featuring an extendedoligophenyleneethynylene-derived π-surface appended withsix long (dodecyloxy (2)) or short (methoxy (3)) side groups.Complex 2, containing dodecyloxy chains, forms fibrous assemblies with a slipped arrangement of the monomer units (dPt···Pt… =14 Å) in both nonpolar solvents and the solid state.Dispersion-corrected PM6 calculations suggest that this organizationis driven by cooperative π–π, C-H···Cl and π–Pt interactions, which is supported by EXAFS and 2D NMR spectroscopic analysis. In contrast, nearly parallel π-stacks (dPt···Pt… = 4.4 Å) stabilized by multiple π–π and C-H···Cl contact sare obtained in the crystalline state for 3 lacking longside chains, as shown by X-ray analysis and PM6 calculations.Our results reveal not only the key role of alkyl chain lengthin controlling self-assembly modes but also show the relevanceof Pt-bound chlorine ligands as new supramolecular synthons.

High Pressure Speed of Sound and Related Thermodynamic Properties of 1-Alkyl-3-methylimidazolium Bis[(trifluoromethyl)sulfonyl]imides (from 1-Propyl- to 1-Hexyl-)

The knowledge of thermodynamic high-pressure speed of sound in ionic liquids (ILs) is a crucial way either to study the nature of the molecular interactions, structure and packing effects or to determine other key thermodynamic properties of ILs essential for their applications in any chemical and industrial processes. Herein, we report the speed of sound as a function temperature at pressures up to 101 MPa in four ultrapure ILs: 1-propyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, 1-pentyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, and 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, taking into consideration their relaxation behavior. Additionally, to further improve the reliability of the speed of sound results, the density, isentropic compressibility, and isobaric heat capacity as a function of temperature and pressure are calculated using an acoustic method.

Synthesis and characterization of lanthanum- and yttrium-doped Fe2O3 pigments

MELO, D. M. A. et al. Synthesis and charactezarion of lanthanum and yttrium doped Fe2O3 pigments. Cerâmica, São Paulo, v. 53, p. 79-82, 2007.

Intrinsic gas-phase electrophilic reactivity of Ccclic N-alkyl- and N-acyliminium ions

he intrinsic gas-phase reactivity of cyclic N-alkyl- and N-acyliminium ions toward addition of allyltrimethylsilane (ATMS) has been compared using MS2 and MS3 pentaquadrupole mass spectrometric experiments. An order of electrophilic reactivity has been derived and found to agree with orders of overall reactivity in solution. The prototype five-membered ring N-alkyliminium ion 1a and its N-CH3 analogue 1b, as well as their six-membered ring analogues 1c and 1d, lack N-acyl activation and they are, accordingly, inert toward ATMS addition. The five- and six-membered ring N-acyliminium ions with N-COCH3 exocycclic groups, 3a and 3b, respectively, are also not very reactive. The N-acyliminium ions 2a and 2c, with s-trans locked endocyclic N-carbonyl groups, are the most reactive followed closely by 3c and 3d with exocyclic (and unlocked) N-CO2CH3 groups. The five-membered ring N-acyliminium ions are more reactive than their six-membered ring analogues, that is:  2a > 2c and 3c > 3d. In contrast with the high reactivity of 2a, its N-CH3 analogue 2b is inert toward ATMS addition. For the first time, the transient intermediates of a Mannich-type condensation reaction were isolatedthe β-silyl cations formed by ATMS addition to N-acyliminium ionsand their intrinsic gas-phase behavior toward dissociation and reaction with a nucleophile investigated. When collisionally activated, the β-silyl cations dissociate preferentially by Grob fragmentation, that is, by retro-addition. With pyridine, they react competitively and to variable extents by proton transfer and by trimethylsilylium ion abstractionthe final and key step postulated for α-amidoalkylation. Becke3LYP/6-311G(d,p) reaction energetics, charge densities on the electrophilic C-2 site, and AM1 LUMO energies have been used to rationalize the order of intrinsic gas-phase electrophilic reactivity of cyclic iminium and N-acyliminium ions.

Synthesis and characterization of lanthanum- and yttrium-doped Fe2O3 pigments

MELO, D. M. A. et al. Synthesis and charactezarion of lanthanum and yttrium doped Fe2O3 pigments. Cerâmica, São Paulo, v. 53, p. 79-82, 2007.

Effect of the cation on the interactions between alkyl methyl imidazolium chloride ionic liquids and water

A systematic study of the interactions between water and alkyl methyl imidazolium chloride ionic liquids at 298.2 K, based on activity coefficients estimated from water activity measurements in the entire solubility range, is presented. The results show that the activity coefficients of water in the studied ILs are controlled by the hydrophilicity of the cation and the cation-anion interaction. To achieve a deeper understanding on the interactions between water and the ILs, COSMO-RS and FTIR spectroscopy were also applied. COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies, suggesting the formation of complexes between three molecules of water and one IL molecule. On the basis of quantum-chemical calculations, it is found that cation-anion interaction plays an important role upon the ability of the IL anion to interact with water. The changes in the peak positions/band areas of OH vibrational modes of water as a function of IL concentration were investigated, and the impact of the cation on the hydrogen-bonding network of water is identified and discussed.

Thermodynamic Study Of The Micellization Of Zwitterionic Surfactants And Their Interaction With Polymers In Water By Isothermal Titration Calorimetry.

The micellization of a homologous series of zwitterionic surfactants, a group of sulfobetaines, was studied using isothermal titration calorimetry (ITC) in the temperature range from 15 to 65 °C. The increase in both temperature and the alkyl chain length leads to more negative values of ΔGmic(0) , favoring the micellization. The entropic term (ΔSmic(0)) is predominant at lower temperatures, and above ca. 55-65 °C, the enthalpic term (ΔHmic(0)) becomes prevalent, figuring a jointly driven process as the temperature increases. The interaction of these sulfobetaines with different polymers was also studied by ITC. Among the polymers studied, only two induced the formation of micellar aggregates at lower surfactant concentration: poly(acrylic acid), PAA, probably due to the formation of hydrogen bonds between the carboxylic group of the polymer and the sulfonate group of the surfactant, and poly(sodium 4-styrenesulfonate), PSS, probably due to the incorporation of the hydrophobic styrene group into the micelles. The prevalence of the hydrophobic and not the electrostatic contributions to the interaction between sulfobetaine and PSS was confirmed by an increased interaction enthalpy in the presence of electrolytes (NaCl) and by the observation of a significant temperature dependence, the latter consistent with the proposed removal of hydrophobic groups from water.

Membrane Lipid Profile Monitored By Mass Spectrometry Detected Differences Between Fresh And Vitrified In Vitro-produced Bovine Embryos.

Summary This study aimed to evaluate the impact of vitrification on membrane lipid profile obtained by mass spectrometry (MS) of in vitro-produced bovine embryos. Matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) has been used to obtain individual embryo membrane lipid profiles. Due to conditions of analysis, mainly membrane lipids, most favorably phosphatidylcholines (PCs) and sphingomyelins (SMs) have been detected. The following ions described by their mass-to-charge ratio (m/z) and respective attribution presented increased relative abundance (1.2-20×) in the vitrified group: 703.5 [SM (16:0) + H]+; 722.5 [PC (40:3) + Na]+; 758.5 [PC (34:2) + H]+; 762.5 [PC (34:0) + H]+; 790.5 [PC (36:0) + H]+ and 810.5 [PC (38:4) + H]+ and/or [PC (36:1) + Na]+. The ion with a m/z 744.5 [PCp (34:1) and/or PCe (34:2)] was 3.4-fold more abundant in the fresh group. Interestingly, ions with m/z 722.5 or 744.5 indicate the presence of lipid species, which are more resistant to enzymatic degradation as they contain fatty acyl residues linked through ether type bonds (alkyl ether or plasmalogens, indicated by the lowercase 'e' and 'p', respectively) to the glycerol structure. The results indicate that cryopreservation impacts the membrane lipid profile, and that these alterations can be properly monitored by MALDI-MS. Membrane lipids can therefore be evaluated by MALDI-MS to monitor the effect of cryopreservation on membrane lipids, and to investigate changes in lipid profile that may reflect the metabolic response to the cryopreservation stress or changes in the environmental conditions.

Nd:YAG laser irradiation effect on apical intracanal dentin - a microleakage and SEM evaluation

The purpose of this in vitro study was to evaluate the effect of neodymium:yttrium-aluminum-garnet (Nd:YAG) laser irradiation on intracanal dentin surface by SEM analysis and its interference in the apical seal of filled canals. After endodontic treatment procedures, 34 maxillary human incisors were randomly assigned to 2 groups. In the negative control group (n=17), no additional treatment was performed and teeth were filled with vertically condensed gutta-percha; in the laser-treated group (n=17), the root canals were irradiated with Nd:YAG laser (1.5 W, 100 mJ, 15 Hz) before filling as described for the control group. Two specimens of each group were prepared for SEM analysis to evaluate the presence and extent of morphological changes and removal of debris; the other specimens were immersed in 0.5% methylene blue dye (pH 7.2) for 24 h for evaluation of the linear dye leakage at the apical third. SEM analysis of the laser-treated group showed dentin fusion and resolidification without smear layer or debris. The Student’s t-test showed that the laser-treated group had significantly less leakage in apical third than the control group. Within the limitations of this study, it may be concluded that the morphological changes on the apical intraradicular dentin surface caused by Nd:YAG laser resulted in less linear dye apical leakage.

Efficient synthesis of benzothiazine and acrylamide compounds

This article describes the synthesis of the new (2Z)-2-(4-methoxybenzylidene)-6-nitro-4H -benzo[1,4]thiazin-3-one, (2Z)-2-(4-methoxybenzylidene)-4-methyl-6-nitro-4H-benzo[1,4]thiazin-3-one, (2Z)-6-amino-2-(4-methoxybenzylidene)-4H -benzo[1,4]thiazin-3-one, (2Z)-6-butylamino-2-(4-methoxybenzylidene)-4-methyl-4H-benzo[1,4]-thiazin-3-one and (2E)-N-alkyl-N-(2-hydroxy-5-nitrophenyl)-3-phenylacrylamides and the spectroscopic data. The arylidenebenzothiazine compounds were prepared using the Knoevenagel condensation with substituted benzaldehydes in the presence of sodium methoxide in DMF. The presence of a nitro substituent in the 4-position, water and a slightly acid reaction medium in this condensation caused the rupture of the benzothiazine ring and subsequent formation of the phenylacrylamide compounds. A crystallographic data was presented for (2E)-3-(4-bromophenyl)-N-dodecyl-N -(2-hydroxy-5-nitrophenyl) acrylamide.

Perception of difficulties with vision-related activities of daily living among patients undergoing unilateral posterior capsulotomy

OBJECTIVES: To assess the influence of Nd:YAG (neodymium: yttrium-aluminum- garnet) laser unilateral posterior capsulotomy on visual acuity and patients' perception of difficulties with vision-related activities of daily life. METHODS: We conducted an interventional survey that included 48 patients between 40 and 80 years of age with uni- or bilateral pseudophakia, posterior capsule opacification, and visual acuity <0.30 (logMAR) in one eye who were seen at a Brazilian university hospital. All patients underwent posterior capsulotomy using an Nd:YAG laser. Before and after the intervention, patients were asked to complete a questionnaire that was developed in an exploratory study. RESULTS: Before posterior capsulotomy, the median visual acuity (logMAR) of the included patients was 0.52 (range 0.30-1.60). After posterior capsulotomy, the median visual acuity of the included patients improved to 0.10 (range 0.0-0.52). According to the subjects' perceptions, their ability to perform most of their daily life activities improved after the intervention (p<0.05). CONCLUSIONS: After patients underwent posterior capsulotomy with an Nd:YAG laser, a significant improvement in the visual acuity of the treated eye was observed. Additionally, subjects felt that they experienced less difficulty performing most of their vision-dependent activities of daily living.