Microwave-Assisted Derivatization of Cellulose in an Ionic Liquid: An Efficient, Expedient Synthesis of Simple and Mixed Carboxylic Esters

Microwave (MW)-assisted cellulose dissolution in ionic liquids (ILs) has routinely led either to incomplete biopolymer solubilization, or its degradation. We show that these problems can be avoided by use of low-energy MW heating, coupled with efficient stirring. Dissolution of microcrystalline cellulose in the IL 1-allyl-3-methylimidazolium chloride has been achieved without changing its degree of polymerization; regenerated cellulose showed pronounced changes in its index of crystallinity, surface area, and morphology. MW-assisted functionalization of MCC by ethanoic, propanoic, butanoic, pentanoic, and hexanoic anhydrides has been studied. Compared with conventional heating, MW irradiation has resulted in considerable decrease in dissolution and reaction times. The value of the degree of substitution (DS) was found to be DS(ethanoate) > DS(propanoate) > DS(butanoate). The values of DS(pentanoate) and DS(hexanoate) were found to be slightly higher than DS(ethanoate). This surprising dependence on the chain length of the acylating agent has been reported before, but not rationalized. On the basis of the rate constants and activation parameters of the hydrolysis of ethanoic, butanoic, and hexanoic anhydrides in aqueous acetonitrile (a model acyl transfer reaction), we suggest that this result may be attributed to the balance between two opposing effects, namely, steric crowding and (cooperative) hydrophobic interactions between the anhydride and the cellulosic surface, whose lipophilicity has increased, due to its partial acylation. Four ethanoate-based mixed esters were synthesized by the reaction with a mixture of the two anhydrides; the ethanoate moiety predominated in all products. The DS is reproducible and the IL is easily recycled. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 134-143, 2010

Surface esterification of cellulose fibres: Processing and characterisation of low-density polyethylene/cellulose fibres composites

Low-density polyethylene was filled with cellulose fibres from sugar cane bagasse obtained from organosolv/supercritical carbon dioxide pulping process. The fibres were also used after chemical modification with octadecanoyl and dodecanoyl chloride acids. The morphology, thermal properties, mechanical properties in both the linear and nonlinear range, and the water absorption behaviour of ensuing composites were tested. The evidence of occurrence of the chemical modification was checked by X-ray photoelectron spectrometry. The degree of polymerisation of the fibres and their intrinsic properties (zero tensile strength) were determined. It clearly appeared that the surface chemical modification of cellulose fibres resulted in improved interfacial adhesion with the matrix and higher dispersion level. However, composites did not show improved mechanical performances when compared to unmodified fibres. This surprising result was ascribed to the strong lowering of the degree of polymerisation of cellulose fibres (as confirmed by the drastic decrease of their zero tensile strength) after chemical treatment despite the mild conditions used. (c) 2007 Elsevier Ltd. All rights reserved.

Effects of Cobalt Chloride in Junctional Epithelium and Reduced Enamel Epithelium of the Rat Maxillary First Molar

Cobalt is one of the main components of cast metal alloys broadly used in dentistry. It is the constituent of 45 to 70% of numerous prosthetic works. There are evidences that metal elements cause systemic and local toxicity. The purpose of the present study was to evaluate the effects of cobalt on the junctional epithelium and reduced enamel epithelium of the first superior molar in rats, during lactation. To do this, 1-day old rats were used, whose mothers received 300mg of cobalt chloride per liter of distilled water in the drinker, during lactation. After 21 days, the rat pups were killed with an anesthetic overdose. The heads were separated, fixed in ""alfac"", decalcified and embedded in paraffin. Frontal sections stained with hematoxylin and eosin were employed. Karyometric methods allowed to estimate the following parameters: biggest, smallest and mean diameters, D/d ratio, perimeter, area, volume, volume/area ratio, eccentricity, form coefficient and contour index. Stereologic methods allow to evaluate: cytoplasm/nucleus ratio, cell and cytoplasm volume, cell number density, external surface/basal membrane ratio, thickness of the epithelial layers and surface density. All the collected data were subjected to statistic analysis by the non-parametric Wilcoxon-Mann-Whitney test. The nuclei of the studied tissues showed smaller values after karyometry for: diameters; perimeter, area, volume and volume/area ratio. Stereologically, it was observed, in the junctional epithelium and in the reduced enamel epithelium, smaller cells with scarce cytoplasm, reflected in the greater number of cells per mm3 of tissue. In this study, cobalt caused epithelial atrophy, indicating a direct action on the junctional and enamel epithelium.

4-Fluoro-2-methoxyphenol, an apocynin analog with enhanced inhibitory effect on leukocyte oxidant production and phagocytosis

Apocynin, a methoxy-substituted catechol (4-hydroxy-3-methoxyacetophenone), originally extracted from the roots of Picrorhiza kurroa, has been extensively used as a non-toxic inhibitor of the multienzymatic complex NADPH oxidase. We discovered that the analogous methoxy-substituted catechol, 4-Fluoro-2-methoxyphenol (F-apocynin), in which the acetyl group present in apocynin was changed to a fluorine atom, was significantly more potent as an inhibitor of NADPH oxidase activity, myeloperoxidase (MPO) chlorinating activity and phagocytosis of microorganisms by neutrophils; it was also as potent as apocynin in inhibiting tumor necrosis factor-alpha (TNF alpha) release by peripheral blood mononuclear cells. We attribute the increased potency of F-apocynin to its increased lipophilicity, which could facilitate the passage of the drug through the cell membrane. The inhibition of MPO chlorination activity, phagocytosis and TNF alpha release shows that apocynin and F-apocynin actions are not restricted to reactive oxygen species inhibition, but further studies are needed to clarify if these mechanisms are related. Like apocynin, F-apocynin did not show cell toxicity, and is a strong candidate for use in the treatment of inflammatory diseases. (C) 2011 Elsevier B.V. All rights reserved.

Investigation of AISI 1040 steel corrosion H(2)S solution containing chloride ions by digital image processing coupled with in electrochemical techniques

This paper presents a study of AISI 1040 steel corrosion in aqueous electrolyte of acetic acid buffer containing 3.1 and 31 x 10(-3) mol dm(-3) of Na(2)S in both the presence and absence of 3.5 wt.% NaCl. This investigation of steel corrosion was carried out using potential polarization, and open-circuit and in situ optical microscopy. The morphological analysis and classification of types of surface corrosion damage by digital image processing reveals grain boundary corrosion and shows a non-uniform sulfide film growth, which occurs preferentially over pearlitic grains through successive formation and dissolution of the film. (C) 2011 Elsevier Ltd. All rights reserved.

Sol-gel prepared AlPO(4) with incorporating Rhodamine 6G

Rhodamine 6G (RH6G) laser dye-doped AlPO(4) xerogel and glass were prepared via a simple sol-gel route by one-step process and two-step process, respectively. The aggregating behavior of dyes in xerogel and glass was studied by excitation and emission spectra. The results indicated the dye aggregates become significantly weak in AlPO(4) glass than in xerogel, which might be attributed to the enhanced interactions between dye and AlPO(4) network as well as the nano-scale separation of dye by the mesoporous structure of AlPO(4) glass. The (27)Al MAS NMR of AlPO(4) glass confirms the interaction of RH6G with AlPO(4) glass network. Incorporation of RH6G into AlPO(4) glass converts Al(4) to Al(6) units, resulting in the increase of Al(6) concentration with the doped RH6G concentration. (C) 2010 Elsevier B.V. All rights reserved.

Fluorescent AlPO(4) gels and glasses doped with Rhodamine 6G: Preparation, structural and optical characterization

Fluorescent AlPO(4) xerogels doped with different amounts of Rhodamine 6G (Rh6G) laser dye were prepared by a one-step sal-gel process. In addition, mesoporous AlPO(4) glasses obtained from undoped gels were loaded with different amounts of Rh6G by wet impregnation. Optical excitation and emission spectra of both series of samples show significant dependences on Rh6G concentration, revealing the influence of dye molecular aggregation. At comparable dye concentrations the aggregation effects are found to be significantly stronger in the gels than in the mesoporous glasses. This effect might be attributed to stronger interactions between the dye molecules and the glass matrix, resulting in more efficient dye dispersion in the latter. The interaction of Rh6G with the glassy AlPO(4) network has been probed by (27)Al and (31)P solid-state NMR techniques. New five- and six-coordinated aluminum environments have been observed and characterized by advanced solid-state NMR techniques probing (27)Al-(1)H and (27)Al-(31)P internuclear dipole couplings. The fractional area of these new Al sites is correlated with the combined fractional area of two new Q(3Al)((0)) and Q(2Al)((0)) phosphate species observed in the (31)P MAS NMR spectra. Based on this correlation as well as detailed composition dependent studies, we suggest that the new signals arise from the breakage of Al-O-P linkages associated with the insertion process. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, characterization, and single crystal X-ray structure of the 1-furoyl-3-cyclohexylthiourea cadmium chloride complex, Cd[C4H3OC(O)NHC(S)NHC6H11]4Cl2

Cadmium chloride complex of 1-furoyl-3-cyclohexylthiourea (CyTu) was prepared and characterized by elemental analysis, IR, and Raman spectroscopy. The structure of the complex was determined by single crystal X-ray methods (space group Bbab, a = 20.918(1), b = 23.532(1), c = 23.571(1) angstrom, = = , Z = 8). Each cadmium has distorted octahedral geometry, coordinated by two chlorides and the thiocarbonyl sulfurs from four CyTu molecules. All the spectroscopic data are consistent with coordination of CyTu by sulfur to cadmium.

Acetyl Radical Production by the Methylglyoxal-Peroxynitrite System: A Possible Route for L-Lysine Acetylation

Methylglyoxal is an a-oxoaldehyde putatively produced in excess from triose phosphates, aminoacetone, and acetone in some disorders, particularly in diabetes. Here, we investigate the nucleophilic addition of ONOO(-), known as a potent oxidant and nucleophile, to methylglyoxal, yielding an acetyl radical intermediate and ultimately formate and acetate ions. The rate of ONOO(-) decay in the presence of methylglyoxal [k(2,app) = (1.0 +/- 0.1) x 10(3) M(-1) s(-1); k(2) approximate to 1.0 x 10(5) M(-1) s(-1)] at pH 7.2 and 25 degrees C was found to be faster than that reported with monocarbonyl substrates (k(2) < 10(3) M(-1) diacetyl (k(2) = 1.0 x 10(4) M(-1) s(-1)), or CO(2) (k(2) = 3-6 x 10(4) M(-1) s(-1)). The pH profile of the methylglyoxal peroxynitrite reaction describes an ascendant curve with an inflection around pH 7.2, which roughly coincides with the pK(a) values of both ONOOH and H(2)PO(4)(-) ion. Electron paramagnetic resonance spin trapping experiments with 2-methyl-2-nitrosopropane revealed concentration-dependent formation of an adduct that can be attributed to 2-methyl-2-nitrosopropane-CH(3)CO(center dot) (a(N) = 0.83 mT). Spin trapping with 3,5-dibromo-4-nitrosobenzene sulfonate gave a signal that could be assigned to a methyl radical adduct [a(N) = 1.41 mT; a(H) = 1.35 mT; a(H(m)) = 0.08 mT]. The 2-methyl-2-nitrosopropane-CH(3)CO(center dot) adduct could also be observed by replacement of ONOO(-) with H(2)O(2), although at much lower yields. Acetyl radicals could be also trapped by added L-lysine as indicated by the presence of W-acetyl-L-lysine in the spent reaction mixture. This raises the hypothesis that ONOO(-)/H(2)O(2) in the presence of methylglyoxal is endowed with the potential to acetylate proteins in post-translational processes.

Unraveling Dynamical Heterogeneity in the Ionic Liquid 1-Butyl-3-methylimidazolium Chloride

Heterogeneous dynamics within a time range of nanoseconds was investigated by molecular dynamics (MD) simulations of 1 -butyl-3-methylimidazolium chloride ([bmim]Cl). After identifying groups of fast and slow ions, it was shown that the separation between the location of the center of mass and the center of charge of cations, d(CMCC), is a signature of such difference in ionic mobility. The distance d(CMCC) can be used as a signature because it relaxes in the time window of the dynamical heterogeneity. The relationship between the parameter dcmcc and conformations of the side alkyl chain in [bmim] is discussed. Since the relatively slow relaxation of dcmcc is a consequence of coexisting polar and nonpolar domains in the bulk, the MD simulations reveal a subtle interplay between structural and dynamical heterogeneity in ionic liquids.

Differential Acetyl Cholinesterase Inhibition by Volatile Oils from two Specimens of Marlierea racemosa (Myrtaceae) Collected from Different Areas of the Atlantic Rain Forest

The volatile oil composition and anti-acetyl cholinesterase activity were analyzed in two specimens of Marlierea racemosa growing in different areas of the Atlantic Rain Forest (Cananeia and Caraguatatuba, SP, Brazil). Component identifications were performed by GUMS and their acetyl cholinesterase inhibitory activity was measured through colorimetric analysis. The major constituent in both specimens was spathulenol (25.1 % in Cananeia and 31.9% in Caraguatatuba). However, the first one also presented monoterpenes (41.2%), while in the Carguatatuba plants, this class was not detected. The oils from the plants collected in Cananeia were able to inhibit the acetyl cholinesterase activity by LIP to 75%, but for oils from the other locality the maximal inhibition achieved was 35%. These results suggested that the monoterpenes are more effective in the inhibition of acetyl cholinesterase activity than sesquiterpenes as these compounds are present in higher amounts in the M. racemosa plants collected in Cananeia.

The influence of albumin on the anodic dissolution of chromium present in UNSS31254 stainless steel in chloride environment

The influence of bovine serum albumin (BSA) on the anodic dissolution of chromium present in UNS S31254 stainless steel (SS) in 0.15 mol L-1 NaCl at 37.0 +/- 0.5 degrees C has been studied, using anodic potentiostatic polarization curves and optical emission spectroscopy. Electrochemical results have shown that BSA has little effect on the transpassivation potential (E-T) and on the passivation current density values. However on the passivation range, BSA diminishes the intensity of the anodic wave seen at about E=750mV versus SCE attributed to Cr(III)/Cr(VI) oxidation. Optical emission spectroscopy results have shown that BSA prevents the anodic dissolution of chromium to occur and minimizes iron dissolution above the transpassivation potential (E=1160 mV versus SCE). (C) 2007 Elsevier B.V. All rights reserved.

Application of 1-Allyl-3-(1-butyl)imidazolium Chloride in the Synthesis of Cellulose Esters: Properties of the Ionic Liquid, and Comparison with Other Solvents

The ionic liquid (IL), 1-allyl-3-(1-butyl)imidazolium chloride (AlBuImCl), has been synthesized and its properties determined. Increase in the temperature increased its conductivity and decreased its density, polarity, and viscosity. Microcrystalline cellulose (MCC), dissolves in thisIL by heating at 80 degrees C; this did not affect its degree of polymerization, decreased its index of crystallinity (Ic), and changed in morphology after regeneration. Convenient acylation of MCC was achieved by using 50% excess anhydride at 80 degrees C, for 24 or 48 h for acetic and butyric anhydride, respectively. The composition of the mixed esters depended on the initial ratio of the anhydrides, and their order of addition.

Thermo-solvatochromism of merocyanine polarity probes - What are the consequences of increasing probe lipophilicity through annelation?

The question raised in the title has been answered by comparing the solvatochromism of two series of polarity probes, the lipophilicities of which were increased either by increasing the length of an alkyl group (R) attached to a fixed pyridine-based structure or through annelation (i.e., by fusing benzene rings onto a central pyridine-based structure). The following novel solvatochromic probes were synthesized: 2,6-dibromo-4-[(E)-2-(1-methylquinolinium-4-yl)ethenyl]-phenolate (MeQMBr(2)) and 2,6-dibromo-4-[(E)-2-(1-methyl-acridinium-4- yl) ethenyl)]phenolate (MeAMBr(2) The solvatochromic behavior of these probes, along with that of 2,6dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl]phenol-ate(MePMBr(2)) was analyzed in terms of increasing probe lipophilicity, through annelation. Values of the empirical solvent polarity scale [E(T)(MePMBr(2))] in kcalmol(-1) correlated linearly with ET(30), the corresponding values for the extensively employed probe 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (RB). On the other hand, the nonlinear correlations of ET(MeQMBr(2)) or ET(MeAMBr(2)) with E(T)(30) are described by second-order polynomials. Possible reasons for this behavior include: i) self-aggregation of the probe, ii) photoinduced cis/trans isomerization of the dye, and iii) probe structure- and solvent-dependent contributions of the quinonoid and zwitterionic limiting formulas to the ground and excited states of the probe. We show that mechanisms (i) and (ii) are not operative under the experimental conditions employed; experimental evidence (NMR) and theoretical calculations are presented to support the conjecture that the length of the central ethenylic bond in the dye increases in the order MeAMBr(2) > MeQMBr(2) > MePMBr(2), That is, the contribution of the zwitterionic limiting formula predominates for the latter probe, as is also the case for RB, this being the reason for the observed linear correlation between the ET(MePMBr2) and the ET(30) scales. The effect of increasing probe lipophilicity on solvatochromic behavior therefore depends on the strategy employed. Increasing the length of R affects solvatochromism much less than annelation, because the former structural change hardly perturbs the energy of the intramolecular charge-transfer transition responsible for solvatochromism. The thermo-solvatochromic behavior (effect of temperature on solvatochromism) of the three probes was studied in mixtures of water with propanol and/or with DMSO. The solvation model used explicitly considers the presence of three ""species"" in the system: bulk solution and probe solvation shell [namely, water (W), organic solvent (Solv)], and solvent-water hydrogen-bonded aggregate (Solv-W). For aqueous propanol, the probe is efficiently solvated by Solv-W; the strong interaction of DMSO with W drastically decreases the efficiency of Solv-W in solvating the probe, relative to its precursor solvents. Temperature increases resulted in desolvation of the probes, due to the concomitant reduction in the structured characters of the components of the binary mixtures.

Micellar properties of surface active ionic liquids: A comparison of 1-hexadecyl-3-methylimidazolium chloride with structurally related cationic surfactants

Ionic liquids, ILs, carrying long-chain alkyl groups are surface active, SAIIs. We investigated the micellar properties of the SAIL 1-hexadecyl-3-methylimidazolium chloride, C(16)MeImCl, and compared the data with 1-hexadecylpyridinium chloride, C(16)PYCl, and benzyl (3-hexadecanoylaminoethyl)dimethylammonium chloride, C(15)AEtBzMe(2)Cl. The properties compared include critical micelle concentration, cmc; thermodynamic parameters of micellization; empirical polarity and water concentrations in the interfacial regions. In the temperature range from 15 to 75 degrees C, the order of cmc in H(2)O and in D(2)O is C(16)PYCl > C(16)MeImCl > C(15)AEtBzMe(2)Cl. The enthalpies of micellization, Delta H(mic)(degrees), were calculated indirectly from by use of the van`t Hoff treatment; directly by isothermal titration calorimetry, ITC. Calculation of the degree of counter-ion dissociation, alpha(mic), from conductivity measurements, by use of Evans equation requires knowledge of the aggregation numbers, N(agg), at different temperatures. We have introduced a reliable method for carrying out this calculation, based on the volume and length of the monomer, and the dependence of N(agg) on temperature. The N(agg) calculated for C(16)PyCl and C(16)MeImCl were corroborated by light scattering measurements. Conductivity- and ITC-based Delta H(mic)(degrees) do not agree; reasons for this discrepancy are discussed. Micelle formation is entropy driven: at all studied temperatures for C(16)MeImCl; only up to 65 degrees C for C(16)PyCl; and up to 55 degrees C for C(15)AEtBzMe(2)Cl. All these data can be rationalized by considering hydrogen-bonding between the head-ions of the monomers in the micellar aggregate. The empirical polarities and concentrations of interfacial water were found to be independent of the nature of the head-group. (C) 2010 Elsevier Inc. All rights reserved.