Thermo-sensitive chitosan-cellulose derivative hydrogels: swelling behaviour and morphologic studies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Carbon nanotubes as reinforcement of cellulose liquid crystalline responsive networks

The incorporation of small amount of highly anisotropic nanoparticles into liquid crystalline hydroxypropylcellulose (LC-HPC) matrix improves its response when is exposed to humidity gradients due to an anisotropic increment of order in the structure. Dispersed nanoparticles give rise to faster order/disorder transitions when exposed to moisture as it is qualitatively observed and quantified by stress-time measurements. The presence of carbon nanotubes derives in a improvement of the mechanical properties of LC-HPC thin films.

Rheo-optical characterization of liquid crystalline acetoxypropylcellulose melt undergoing large shear flow and relaxation after flow cessation

The rheological and structural characteristics of acetoxypropylcellulose (APC) nematic melt are studied at shear rates ranging from 10 s(-1) to 1000 s(-1) which are relevant to extrusion based processes. APC shows a monotonic shear thinning behavior over the range of shear rates tested. The negative extrudate-swell shows a minimum when a critical shear rate (gamma) over dot(c) is reached. For shear rates smaller than (gamma) over dot(c), the flow-induced texture consists of two set of bands aligned parallel and normal to the flow direction. At shear rates larger than (gamma) over dot(c), the flow induced texture is reminiscent of a 2 fluids structure. Close to the shearing walls, domains elongated along the flow direction and stacked along the vorticity are imaged with POM, whereas SALS patterns indicate that the bulk of the sheared APC is made of elliptical domains oriented along the vorticity. No full nematic alignment is achieved at the largest shear rate tested. Below (gamma) over dot(c), the stress relaxation is described by a stretched exponential. Above (gamma) over dot(c), the stress relaxation is described by a fast and a slow process. The latter coincides with the growth of normal bands thicknesses, as the APC texture after flow cessation consists of two types of bands with parallel and normal orientations relative to the flow direction. Both bands thicknesses do not depend on the applied shear rate, in contrast to their orientation. (C) 2015 Elsevier Ltd. All rights reserved.

Development of a colorimetric indicator label for food oxidation based on hexanal detection

In this work, a colorimetric indicator for food oxidation based on the detection of hexanal in gas-phase, has been developed. In fact, in recent years, the food packaging industry has evolved towards new generation of packaging, like active and intelligent. According to literature (Pangloli P. et al. 2002), hexanal is the main product of a fatty acid oxidation: the linoleic acid. So, it was chosen to analyse two kinds of potato chips, fried in two different oils with high concentration of linoleic acid: olive oil and sunflower oil. Five different formulas were prepared and their colour change when exposed to hexanal in gas phase was evaluated. The formulas evaluations were first conducted on filter paper labels. The next step was to select the thickener to add to the formula, in order to coat a polypropylene film, more appropriate than the filter paper for a production at industrial scale. Three kinds of thickeners were tested: a cellulose derivative, an ethylene vinyl-alcohol and a polyvinyl alcohol. To obtain the final labels with the autoadhesive layer, the polypropylene film with the selected formula and thickener was coat with a water based adhesive. For both filter paper and polypropylene labels, with and without autoadhesive layer, the detection limit and the detection time were measured. For the selected formula on filter paper labels, the stability was evaluated, when conserved on the dark or on the light, in order to determine the storage time. Both potato chips samples, stocked at the same conditions, were analysed using an optimised Headspace-Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry (HS-SPME-GC-MS) method, in order to determine the concentration of volatilized hexanal. With the aim to establish if the hexanal can be considered as an indicator of the end of potato chips shelf life, sensory evaluation was conducted each day of HS-SPME-GC-MS analysis.

Employing perichromism for probing the properties of carboxymethyl cellulose films: an expedient, accurate method for the determination of the degree of substitution of the biopolymer derivative

The properties of films of carboxymethyl cellulose, CMC, of different degree of substitution, DS, have been examined by the use of perichromic indicators (probes). The film properties that have been determined are: empirical polarity, E-T(33); "acidity", alpha; "basicity", beta; and dipolarity/polarizability, pi*. This has been achieved by employing the following perichromic probes: 4-nitroaniline, 4-nitroanisole, 4-nitro-N,N-dimethylaniline, and 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate, WB. The correlations between both E-T(33)- or pi* and DS were found to be linear; that between beta and DS is a second order polynomial; no obvious correlation was found between alpha and DS. The polarities of CMC films are in the range of those of butyl alcohols. As models for CMC, we have employed cellulose plus CMC of high DS; oxidized cellulose with degree of oxidation = 0.5; sodium glucuronate. The former model behaved akin to CMC, but the plots of the perichromic properties versus DS showed different slopes/intercepts. FTIR data and molecular dynamics simulations on the solvation of WB have shown that this difference can be traced to more efficient hydrogen bonding between the film of the model and the probe. This affects the intra-molecular charge-transfer energy of the latter, leading to different responses to the variation of DS. Based on the excellent linear correlation between E-T(33) and DS, for CMC from different origins, we suggest that perichromism is a simple, accurate, and expedient alternative for the determination of DS of the biopolymer derivative.

Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films

CH, Chitosan; HPMC, (Hydroxypropyl)methyl cellulose; FT, Freeze-thaw; SC, Solvent casting; CH:HPMC (X:Y), pH Z, FT/SC, Chitosan and (hydroxypropyl)methyl cellulose hydrogel, at X and Y proportion (0-100), at Z pH (3.0-4.0) and prepared by freeze-thaw or solvent casting techniques; DSC, Differential scanning calorimetry; MDSC, Temperature modulated Differential scanning calorimetry; Tg, glass transition temperature; ΔH, enthalpy change; TGA, Thermogravimetric Analysis; TG, Thermogravimetry; DTG, Derivative or Differential thermogravimetry; σ, Tensile strength; ε, elongation at break; DMA, Dynamic mechanical analysis; X-Ray, X-radiation, FTIR-ATR, Attenuated total reflectance Fourier transform infrared spectroscopy; SEM, Scanning electron microscopy.

Erratum to: Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films

CH, Chitosan; HPMC, (Hydroxypropyl)methyl cellulose; FT, Freeze-thaw; SC, Solvent casting; CH:HPMC (X:Y), pH Z, FT/SC, Chitosan and (hydroxypropyl)methyl cellulose hydrogel, at X and Y proportion (0-100), at Z pH (3.0-4.0) and prepared by freeze-thaw or solvent casting techniques; DSC, Differential scanning calorimetry; MDSC, Temperature modulated Differential scanning calorimetry; Tg, glass transition temperature; ΔH, enthalpy change; TGA, Thermogravimetric Analysis; TG, Thermogravimetry; DTG, Derivative or Differential thermogravimetry; σ, Tensile strength; ε, elongation at break; DMA, Dynamic mechanical analysis; X-Ray, X-radiation, FTIR-ATR, Attenuated total reflectance Fourier transform infrared spectroscopy; SEM, Scanning electron microscopy.

Thermal decomposition of microcrystalline cellulose and its pure and containing adsorbed cadmium cations derivatives.

We have studied the thermal decomposition of the microcrystalline cellulose and some of its derivative such as pure carboxymethylcellulose (CMCH), phosphate cellulose (FOSCEL) and oxycellulose (OXICEL) and also these same derivatives containing adsorbed cadmium cations. We have used the TG,DTG tecniques in order to determine the quantity of retained cadmium II cations on the surface of these adsorbents.

Dispersed lipid liquid crystalline phases stabilized by a hydrophobically modified cellulose

Aqueous dispersions of monoolein (MO) with a commercial hydrophobically modified ethyl hydroxyethyl cellulose ether (HMEHEC) have been investigated with respect to the morphologies of the liquid crystalline nanoparticles. Only very low proportions of HMEHEC are accepted in the cubic and lamellar phases of the monoolein-water system. Due to the broad variation of composition and size of the commercial polymer, no other single-phase regions were found in the quasi-ternary system. Interactions of MO with different fractions of the HMEHEC sample induced the formation of lamellar and reversed hexagonal phases, identified from SAXD, polarization microscopy, and cryogenic TEM examinations. In excess water (more than 90 wt %) coarse dispersions are formed more or less spontaneously, containing particles of cubic phase from a size visible by the naked eye to small particles observed by cryoTEM. At high polymer/MO ratios, vesicles were frequently observed, often oligo-lamellar with inter-lamellar connections. After homogenization of the coarse dispersions in a microfluidizer, the large particles disappeared, apparently replaced by smaller cubic particles, often with vesicular attachments on the surfaces, and by vesicles or vesicular particles with a disordered interior. At the largest polymer contents no proper cubic particles were found directly after homogenization but mainly single-walled defected vesicles with a peculiar edgy appearance. During storage for 2 weeks, the dispersed particles changed toward more well-shaped cubic particles, even in dispersions with the highest polymer contents. In some of the samples with low polymer/MO ratio, dispersed particles of the reversed hexagonal type were found. A few of the homogenized samples were freeze-dried and rehydrated. Particles of essentially the same types, but with a less well-developed cubic character, were found after this treatment. © 2007 American Chemical Society.

Thermal behavior of lignin and cellulose from waste composting process

The lignin and cellulose were extracted from reference material (leaves and twigs) and food of compost at different times composting: zero (raw), 30, and 120 days. According to thermogravimetric analysis and its derivative and differential scanning calorimetry curves for these samples, were verified during composting process there were considerable changes in its thermal profiles, as well as, characteristics lignin in cellulose samples and cellulose in lignin samples. These features were found by fourier transformed infrared spectroscopy. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Cellulose based Lithium ion polymer electrolytes for Lithium batteries

The separator membrane in batteries and fuel cells is of crucial importance for the function of these devices. In lithium ion batteries the separator membrane as well as the polymer matrix of the electrodes consists of polymer electrolytes which are lithium ion conductors. To overcome the disadvantage of currently used polymer electrolytes which are highly swollen with liquids and thus mechanically and electrochemically unstable, the goal of this work is a new generation of solid polymer electrolytes with a rigid backbone and a soft side chain structure. Moreover the novel material should be based on cheap substrates and its synthesis should not be complicated aiming at low overall costs. The new materials are based on hydroxypropylcellulose and oligoethyleneoxide derivatives as starting materials. The grafting of the oligoethyleneoxide side chains onto the cellulose was carried out following two synthetic methods. One is based on a bromide derivative and another based on p-toluolsulfonyl as a leaving group. The side chain reagents were prepared form tri(ethylene glycol) monoethyl ether. In order to improve the mechanical properties the materials were crosslinked. Two different conceptions have been engaged based on either urethane chemistry or photosensitive dimethyl-maleinimide derivatives. PEO - graft - cellulose derivatives with a high degree of substitution between 2,9 and 3,0 were blended with lithium trifluoromethane-sulfonate, lithium bis(trifluorosulfone)imide and lithium tetrafluoroborate. The molar ratios were in the range from 0,02 to 0,2 [Li]/[O]. The products have been characterized with nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and laserlight scattering (LS) with respect to their degree of substitution and molecular weight. The effect of salt concentration on ionic conductivity, thermal behaviour and morphology has been investiga-ted with impedance spectroscopy, differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The crosslinking reactions were controlled with dynamic mechanical analysis (DMS). The degree of substitution of our products is varying between 2,8 and 3,0 as determined by NMR. PEO - graft - cellulose derivatives are highly viscous liquids at room temperature with glass transition temperatures around 215 K. The glass transition temperature for the Lithium salt complexes of PEO - graft - cellulose deri-vatives increase with increasing salt content. The maximum conductivity at room temperature is about 10-4 and at 100°C around 10-3 Scm-1. The presence of lithium salt decreases the thermal stability of the complexes in comparison to pure PEO - graft - cellulose derivatives. Complexes heated over 140 – 150°C completely lose their ionic conductivity. The temperature dependence of the conductivity presented as Arrhenius-type plots for all samples is similar in shape and follows a VTF behaviour. This proofs that the ionic transport is closely related to the segmental motions of the polymer chains. Novel cellulose derivatives with grafted oligoethylen-oxide side chains with well-defined chemical structure and high side chain grafting density have been synthesized. Cellulose was chosen as stiff, rod like macromolecule for the backbone while oligoethylen-oxides are chosen as flexible side chains. A maximum grafting density of 3.0 have been obtained. The best conductivity reaches 10-3 Scm-1 at 100°C for a Li-triflate salt complex with a [Li]/[O] ratio of 0.8. The cross-linked complexes containing the lithium salts form elastomeric films with convenient mechanical stability. Our method of cellulose modification is based on relatively cheap and commercially available substrates and as such appears to be a promising alternative for industrial applications.

Drying process of microcrystalline cellulose studied by attenuated total reflection IR spectroscopy with two-dimensional correlation spectroscopy and principal component analysis

Molecular interactions between microcrystalline cellulose (MCC) and water were investigated by attenuated total reflection infrared (ATR/IR) spectroscopy. Moisture-content-dependent IR spectra during a drying process of wet MCC were measured. In order to distinguish overlapping O–H stretching bands arising from both cellulose and water, principal component analysis (PCA) and, generalized two-dimensional correlation spectroscopy (2DCOS) and second derivative analysis were applied to the obtained spectra. Four typical drying stages were clearly separated by PCA, and spectral variations in each stage were analyzed by 2DCOS. In the drying time range of 0–41 min, a decrease in the broad band around 3390 cm−1 was observed, indicating that bulk water was evaporated. In the drying time range of 49–195 min, decreases in the bands at 3412, 3344 and 3286 cm−1 assigned to the O6H6cdots, three dots, centeredO3′ interchain hydrogen bonds (H-bonds), the O3H3cdots, three dots, centeredO5 intrachain H-bonds and the H-bonds in Iβ phase in MCC, respectively, were observed. The result of the second derivative analysis suggests that water molecules mainly interact with the O6H6cdots, three dots, centeredO3′ interchain H-bonds. Thus, the H-bonding network in MCC is stabilized by H-bonds between OH groups constructing O6H6cdots, three dots, centeredO3′ interchain H-bonds and water, and the removal of the water molecules induces changes in the H-bonding network in MCC.

Oxygen isotope ratios of cellulose-derived phenylglucosazone: An improved paleoclimate indicator of environmental water and relative humidity

Oxygen atoms within fossil wood provide high-resolution records of climate change, particularly for the Quaternary. However, current analysis methods of fossil cellulose do not differentiate between different positions of the oxygen atoms. Here, we propose a refinement to tree-cellulose paleoclimatology modeling, using the cellulose-derived compound phenylglucosazone as the isotopic substrate. Stem samples from trees were collected at northern latitudes as low as 24°37′N and as high as 69°00′N. We extracted stem water and cellulose from each stem sample and analyzed them for their 18O content. In addition, we derived the cellulose to phenylglucosazone, a compound which lacks the oxygen attached to the second carbon of the cellulose–glucose moieties. Oxygen isotope analysis of phenylglucosazone allowed us to calculate the 18O content of the oxygen attached to the second carbon of the cellulose–glucose moieties. By way of these analyses, we tested two hypotheses: first, that the 18O content of the oxygen attached to second carbon will more closely reflect the 18O content of the stem water, and will not resemble the 18O content of either cellulose or its derivative phenylglucosazone. Second, tree-ring models that incorporate the variable oxygen isotope fractionation shown here and elsewhere are more accurate than those that do not. Our first hypothesis was rejected on the basis that the oxygen isotope ratios of the oxygen attached to the second carbon of the glucose moieties had a noisy isotopic signal with a large standard deviation and gave the poorest correlation with the oxygen isotope ratios of stem water. Related to this isotopic noise, we observed that the correlation between oxygen isotope ratios of phenylglucosazone with both stem water and relative humidity were higher than those observed for cellulose. Our hypothesis about tree-ring models which account for changes in the oxygen isotopic fractionation during cellulose synthesis was consistent only for the 18O content of phenylglucosazone. We showed that the tree-ring model based on the 18O content of phenylglucosazone was an improvement over existing models that are based on whole cellulose. Additionally, this approach may be used in other cellulose based archives such as peat deposits and lacustrine sediments.

The Applicability Of Ordered Mesoporous Sba-15 And Its Hydrophobic Glutaraldehyde-bridge Derivative To Improve Ibuprofen-loading In Releasing System.

The mesoporous SBA-15 silica with uniform hexagonal pore, narrow pore size distribution and tuneable pore diameter was organofunctionalized with glutaraldehyde-bridged silylating agent. The precursor and its derivative silicas were ibuprofen-loaded for controlled delivery in simulated biological fluids. The synthesized silicas were characterized by elemental analysis, infrared spectroscopy, (13)C and (29)Si solid state NMR spectroscopy, nitrogen adsorption, X-ray diffractometry, thermogravimetry and scanning electron microscopy. Surface functionalization with amine containing bridged hydrophobic structure resulted in significantly decreased surface area from 802.4 to 63.0 m(2) g(-1) and pore diameter 8.0-6.0 nm, which ultimately increased the drug-loading capacity from 18.0% up to 28.3% and a very slow release rate of ibuprofen over the period of 72.5h. The in vitro drug release demonstrated that SBA-15 presented the fastest release from 25% to 27% and SBA-15GA gave near 10% of drug release in all fluids during 72.5 h. The Korsmeyer-Peppas model better fits the release data with the Fickian diffusion mechanism and zero order kinetics for synthesized mesoporous silicas. Both pore sizes and hydrophobicity influenced the rate of the release process, indicating that the chemically modified silica can be suggested to design formulation of slow and constant release over a defined period, to avoid repeated administration.

A New Goniothalamin N-acylated Aza-derivative Strongly Downregulates Mediators Of Signaling Transduction Associated With Pancreatic Cancer Aggressiveness.

In this study, a novel concise series of molecules based on the structure of goniothalamin (1) was synthesized and evaluated against a highly metastatic human pancreatic cancer cell line (Panc-1). Among them, derivative 8 displayed a low IC50 value (2.7 μM) and its concentration for decreasing colony formation was 20-fold lower than goniothalamin (1). Both compounds reduced the levels of the receptor tyrosine kinase (AXL) and cyclin D1 which are known to be overexpressed in pancreatic cancer cells. Importantly, despite the fact that goniothalamin (1) and derivative 8 caused pancreatic cancer cell cycle arrest and cell death, only derivative 8 was able to downregulate pro-survival and proliferation pathways mediated by mitogen activated protein kinase ERK1/2. Another interesting finding was that Panc-1 cells treated with derivative 8 displayed a strong decrease in the transcription factor (c-Myc), hypoxia-inducible factor-1α (HIF-1α) and vascular endothelial growth factor (VEGF) protein levels. Notably, the molecular effects caused by derivative 8 might not be related to ROS generation, since no significant production of ROS was observed in low concentrations of this compound (from 1.5 up to 3 μM). Therefore, the downregulation of important mediators of pancreatic cancer aggressiveness by derivative 8 reveals its great potential for the development of new chemotherapeutic agents for pancreatic cancer treatment.