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Systemic administration of histone deacetylase inhibitors (HDACi), like valproic acid (VPA), is often associated with rapid drug metabolization and untargeted tissue distribution. This requires high-dose application that can lead to unintended side effects. Hence, drug carrier systems such as nanoparticles (NPs) are developed to circumvent these disadvantages by enhancing serum half-life as well as organ specificity.This chapter gives a summary of the biological characterization of HDACi-coupled NPs in vitro, including investigation of cellular uptake, biocompatibility, as well as intracellular drug release and activity. Suitable methods, opportunities, and challenges will be discussed to provide general guidelines for the analysis of HDACi drug carrier systems with a special focus on recently developed cellulose-based VPA-coupled NPs.

The ability of histone deacetylase inhibitors (HDACi) like valproic acid (VPA) as a therapeutic for inflammatory diseases or cancer has increased the interest in HDACi and their targeted transport to diseased tissues. Administration of VPA immobilized on polymeric carriers was found to be a suitable approach to circumvent drawbacks such as rapid metabolization, short serum half-life, or side effects. Polysaccharides are convenient biopolymeric carriers due to their biocompatibility and biodegradability. Furthermore, the hydroxy-, amino-, or carboxylic groups are predestinated for functionalization. The esterification of three hydroxy groups of cellulose with VPA leads to products having a high amount of VPA loading. Subsequent shaping yielded uniform nanoparticles (NPs) of around 150 nm in size capable of releasing VPA in a controlled way under physiological conditions.

Synthesis possibility of cellulose sulfates with a low and high degree of substitution (DS) by direct homogenous sulfation of cotton cellulose in N,N-dimethylacetamide/lithium chloride (DMA/LiCl) using SO3/pyridine (Py) complex was studied comprehensively. The sulfation reactions were carried at different temperatures, time durations, amount of the sulfating reagent and celluloses with varying weight average degree of polymerization (DPw). It was found that the method is very appropriate to prepare sodium cellulose sulfate (SCS) with low and high DS from celluloses having wide range DPw. Completely water-soluble SCS samples with regulable DS values from 0.23 to 2.56 were obtained. Suitable conditions were proposed to gain high sulfate content and the samples with DS values of 2.16–2.32, and yield of 69.4–77.8% could be prepared in these conditions. Celluloses with low and high DPw values exhibited similar reactivity for sulfation. Precipitation of the product and drastic depolymerization in the polymer chain have not occurred during the reaction.

The biological activity of macrofungal polysaccharides (MFPS) depends on their structural features and is a topic of keen interest for researchers since long time. In this communication, we report a water soluble macrofungal heteropolysaccharide (MFPS1) with a molar weight of ˜145,000 g/mol, obtained through alkali extraction, of the wild mushroom, Marasmiellus palmivorus, with significant immunomodulatory properties. In cancer, after the induction of metastasis, the anticancer immune system becomes unresponsive. By studying cytokine secretion and immune phenotyping, it was observed that MFPS1 reactivated the anticancer immune surveillance system. MFPS1 executed T-cell maturation and activation via M1Φ; and also stimulated natural killer (NK) cell and B-cell population. The entire immune activation pathway corroborates its anticancer activity. The RP-HPLC analysis of hydrolyzed MFPS1 showed arabinose, glucose, galactose and mannose as monosaccharide units. The proposed structure of repeating unit was established from methylation analysis, 1D- and 2D NMR study, HR-MS and MALDI-TOF MS analysis.

The development of bio-based nanoparticles (NPs) as drug containers is of increasing interest to circumvent several obstacles in drug therapy such as rapid drug metabolization, short serum half-life, and unspecific side effects. The histone deacetylase inhibitor valproic acid (VPA) is known for its anti-inflammatory as well as for its anti-cancer activity. Here, recently developed VPA-loaded NPs based on cellulose- and dextran VPA esters were modified with sulfuric acid half ester moieties to improve intracellular drug release. The NPs show rapid cellular uptake, are non-toxic in vitro and in vivo, and able to induce histone H3 hyperacetylation. Thus, they represent a potent drug delivery system for the application in a variety of treatment settings, such as inflammation, sepsis and defined cancer types. In addition, the flexible NP-system offers a broad range of further options for modification, e.g. for targeting strategies and multi-drug approaches.

Mercerized cellulose (alkali cellulose C6H10O5* NaOH) was obtained by treatment of cotton linters (cellulose) with aqueous sodium hydroxide. Cellulose and alkali-cellulose samples with relative density of 78% and 79% were obtained after sintering the material in air at optimal sintering temperatures of 423 K and 473 K, respectively. The electrical properties of the samples were studied by impedance spectroscopy in the frequency range from 13 MHz to 50 Hz at temperatures between 393 K and 493 K. The influence of cellulose mercerization on electrical properties of cotton linters was observed. The cellulose behaves like an electrical insulator. Contrariwise, the alkali-cellulose is a fast-ionic conductor with a conductivity value of σ473 K = 3.22 × 10−6 S cm−1 having activation energies of 0.49 eV and 0.68 eV at temperature range of 393 K–458 K and 459 K–500 K, respectively. The change of activation energy value has been discussed in relation to thermal stability.

To characterize sulfoethyl cellulose el samples, a capillary electrophoresis method was developed and validated sulfoethyl cellulose el was hydrolyzed, and the resulting d-glucose derivatives were analyzed after reductive amination with 4-aminobenzoic acid using 150 mM boric acid, pH 9.5, as background electrolyte at 20°C and a voltage of 28 kV. Peak identification was derived from capillary electrophoresis with mass spectrometry using 25 mM ammonia adjusted to pH 6.2 by acetic acid as electrolyte. Besides mono-, di-, and trisulfoethyl d-glucose small amounts of disaccharides could be identified resulting from incomplete hydrolysis. The linearity of the borate buffer-based capillary electrophoresis method was evaluated using d-glucose in the concentration range of 3.9-97.5 μg/mL, while limits of detection and quantification derived from the signal-to-noise ratio of 3 and 10 were 0.4 ± 0.1 and 1.2 ± 0.3 μg/mL, respectively. Reproducibility and intermediate precision were determined using a hydrolyzed sulfoethyl cellulose el sample and ranged between 0.2 and 8.8% for migration times and between 0.3 and 10.4% for peak area. The method was applied to the analysis of the degree of substitution of synthetic sulfoethyl cellulose el samples obtained by variation of the synthetic process and compared to data obtained by elemental analysis.

The heterogeneous sulfoethylation of cellulose, xylan, α-1,3-glucan, glucomannan, pullulan, curdlan, galactoglucomannan, and agarose was studied using sodium vinylsulfonate (NaVS) as reagent in presence of sodium hydroxide and iso-propanol (i-PrOH) as slurry medium. The influence of the concentration of polymer, water, and NaOH (solid or aqueous solution) on the degree of substitution (DS) was investigated. The sulfoethylation rendered the polysaccharides studied water-soluble. Sulfoethylation of heteropolysaccharides yielded products with higher DS compared to the conversion of homopolysaccharides. Structure characterization was carried out by means of 13C-NMR spectroscopy.

The histone deacetylase inhibitors (HDACi) are potent drugs in the treatment of inflammatory diseases and defined cancer types. However, major drawbacks of HDACi, such as valproic acid (VPA), are limited serum half-life, side effects and the short circulation time. Thus, the immobilization of VPA in a polysaccharide matrix is used to circumvent these problems and to design a suitable nanocarrier system. Therefore, VPA is covalently attached to cellulose and dextran via esterification with degree of substitution (DS) values of up to 2.20. The resulting hydrophobic polymers are shaped to spherical nanoparticles (NPs) with hydrodynamic diameter between 138 to 221 nm and polydispersity indices from 0.064 to 0.094 by nanoprecipitation and emulsification technique. Lipase treatment of the NPs leads to in vitro release of VPA and hence to an inhibition of HDAC2 activity in a HDAC2 assay. NPs are rapidly taken up by HeLa cells and mainly localize in the cytoplasm. The NPs are hemocompatible and nontoxic as revealed by the shell-less hen's egg model.

Oxidation of cellulose is another important synthesis path to modify the properties of the biopolymer to get value-added products.

Cellulose constitutes the most abundant renewable polymer resource available world-wide. It has been estimated that by photosynthesis, 1011 − 1012 t are synthesized annually in a rather pure form, for example in the seed hairs of the cotton plant, but mostly cellulose is combined with lignin and other polysaccharides (hemicelluloses) in the cell wall of woody plants.

The first systematic clarification of the cellulose structure began in 1837 with investigations of the French agricultural chemist Anselme Payen and finally the French Academy named the carbohydrate “Cellulose”.

It is well known that controlling the reactions of cellulose, e.g., its transformation into esters or ethers, is not trivial. The products obtained may exhibit unpredictable, and often irreproducible DS.

Cellulose ethers are of huge importance and produced commercially in large scales; the worldwide consumption of cellulosic ethers in 2006 was estimated to be 637,000 t.

This feature article summarizes recent developments in the field of so-called aminodeoxy cellulose derivatives ("amino celluloses") that are applied for functional surface coating of biofunctional materials. After introducing common manufacturing methods for nanostructurized substrates (material surfaces and nanoparticles) biorelevant amino celluloses are described. It could be demonstrated that cellulose is a unique starting material for chemical modification of hydroxyl groups and the adjacent carbon atom. Amino celluloses are proved to be the modifiable polymer of choice for the biofunctionalization of material surfaces. Amino celluloses possess self assembling properties and may form monolayer composites on a variety of substrate materials.

A round robin on GPC of a wide range of different pulp samples was conducted among leading groups in cellulose analysis. The aim was to survey the status quo of the methods available to date. The pulp samples covered not only fully-bleached dissolving pulps but also bleached paper pulps and one un-bleached sample. The methods applied were current state-of-the-art GPC with RI, MALLS, and viscosimetry detectors. Different dissolution protocols were compared as well. Following from the obtained results, more standardized protocols were proposed for approaches with different equipment (RI or MALLS/RI) and solvent systems (direct dissolution or derivatization). Major influencing factors, such as derivatization compared to direct solution, calibration versus light scattering and in-between lab variation, were discussed.

The synthesis of microcrystalline cellulose (MCC) and 9,10,16-hydroxyhexadecanoic (aleuritic) acid ester-based bioplastics was investigated through acylation in a mixed anhydride (trifluoroacetic acid (TFA)/trifluoroacetic acid anhydride (TFAA)), chloroform co-solvent system. The effects of chemical interactions and the molar ratio of aleuritic acid to the anhydroglucose unit (AGU) of cellulose were investigated. The degree of substitution (DS) of new polymers were characterized by two-dimensional solution-state NMR and ranged from 0.51 to 2.60. The chemical analysis by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the presence of aleuritate groups in the structure induces the formation of new H-bond networks. The tensile analysis and the contact angle measurement confirmed the ductile behavior and the hydrophobicity of the prepared bioplastics. By increasing the aleuritate amounts, the glass transition temperature decreased and the solubility of bioplastic films in most common solvents was improved. Furthermore, this new polymer exhibits similar properties compared to commercial cellulose derivatives., This work was supported by the BIOPROTO project (reference 625297), funded by the European action FP7-PEOPLE.

Sulfoethylated nanofibrillated cellulose (NFCSulf) was produced by an industrially relevant process. The properties of the NFCSulf were compared with those of carboxymethylated nanofibrillated cellulose (NFCCarb), which has been identified as an attractive NFC for several industrial applications. The investigations revealed that NFCSulf is characterized by a higher degree of fibrillation and has superior redispersion properties. Furthermore, NFCSulf displays higher stability in varying pH values as compared to NFCCarb. Hence, NFCSulf may be a more attractive alternative than NFCCarb in applications such as rheological modifiers or adsorbing components in personal care products, in which the performance of NFC must remain unaffected in varying ambient conditions. The superior properties of NFCSulf compared to NFCCarb were proposed to be due to the combination of the unique chemical characteristics of the sulfoethylated reagent, and the larger size of the sulfonate group compared to the carboxymethyl group.

Pseuderanthemum carruthersii (Seem.) Guillaumin is a native tree in Vietnam. The water extract of the leaves from this tree gives a highly viscous product that has been used to heal wounds and treat inflammations. Our previous studies showed that the leaves of P. carruthersii have a high content of polysaccharides. In this study, the structure and influence of the neutral polysaccharide from Pseuderanthemum carruthersii (PCA1) on lipopolysaccharide (LPS)-stimulated RAW264.7 cells were investigated. The PCA1 isolated from P. carruthersii is a galactan-type polysaccharide, containing galactose (77.0%), 3-O-methyl galactose (20.0%), and arabinose (3.0%). Linkage analysis of PCA1 showed that both the 3-O-methyl galactose and galactose were 1,4-linked. The presence of 3-O-methyl galactose units as part of the polysaccharide is important and can be used as a chemotaxonomic marker. The molecular weight of the PCA1 was 170 kDa. A PCA1 concentration of 30&ndash, 40 &mu, g/mL strongly inhibited TNF&alpha, IL-1&beta, and IL-6 inflammatory cytokine production, and reactive oxygen species (ROS) release. PCA1 had inhibitory activities on pro-inflammatory cytokine and ROS release in LPS-stimulated mouse macrophages in vitro through MAPK signaling.

As part of continuing efforts to prepare cellulose and microcrystalline cellulose (MCC) from renewable biomass resources, rice straw and banana plant waste were used as the available agricultural biomass wastes in Egypt. The cellulose materials were obtained in the first step from rice straw and banana plant waste after chemical treatment, mainly applying alkaline-acid or acid-alkaline pulping which was followed by hypochlorite bleaching method. The results indicate a higher α-cellulose content, 66.2 %, in case of acid-alkaline treatment for rice straw compared to 64.7 % in case of alkaline-acid treatment. A low degree of polymerization, 17, was obtained for the cellulose resulting from acid–alkaline treatment for banana plant waste indicating an oligomer and not a polymer, while it reached 178 in case of the cellulose resulting from alkaline–acid treatment for the rice straw. MCC was then obtained by enzymatic treatment of the resulting cellulose. The resulting MCC show an average diameter ranging from 7.6 to 3.6 μm compared to 25.8 μm for the Avicel PH101. On the other hand, the morphological structure was investigated by scanning electron microscopy indicating a smooth surface for the resulting cellulose, while it indicates that the length and the diameter appeared to be affected by the duration of enzyme treatment for the preparation of MCC. Moreover, the morphological shape of the enzyme treated fibers starts to be the same as the Avicel PH101 which means different shapes of MCC can be reached by the enzyme treatment. Furthermore, Fourier transform infrared spectroscopy was used to indicate characteristic absorption bands of the constituents and the crystallinity was evaluated by X-ray diffraction measurements and by iodine absorption technique. The reported crystallinity values were between 34.8 and 82.4 %, for the resulting cellulose and MCC, and the degree of crystallinity ranged between 88.8 and 96.3 % dependent on the X-ray methods and experimental iodine absorption method.

Two 3-O-ethyl-3-O-propyl celluloses of similar ethyl and propyl content prepared under different conditions were analyzed with respect to their substituent distribution in the glucosyl units and along the polymer chain by ESI-MS analysis of labeled oligosaccharides. Both samples showed similar regioselectivity of substitution and random distribution of ethyl and propyl groups over the 3-O-positions. The distribution of all types of glucosyl residues identified by monomer analysis was also random over the cellulose molecules. Comparison of the substitution pattern in the glucosyl units with the pattern expected for the observed regioselectivity showed relative high 2-O-alkylation in spite of protecting group strategy, but no corresponding 2,3-di-O-substitution. This is probably the result of partial silyl migration under the alkaline alkylation conditions.

To characterize sulfoethyl cellulose el samples, a capillary electrophoresis method was developed and validated sulfoethyl cellulose el was hydrolyzed, and the resulting d-glucose derivatives were analyzed after reductive amination with 4-aminobenzoic acid using 150 mM boric acid, pH 9.5, as background electrolyte at 20°C and a voltage of 28 kV. Peak identification was derived from capillary electrophoresis with mass spectrometry using 25 mM ammonia adjusted to pH 6.2 by acetic acid as electrolyte. Besides mono-, di-, and trisulfoethyl d-glucose small amounts of disaccharides could be identified resulting from incomplete hydrolysis. The linearity of the borate buffer-based capillary electrophoresis method was evaluated using d-glucose in the concentration range of 3.9-97.5 μg/mL, while limits of detection and quantification derived from the signal-to-noise ratio of 3 and 10 were 0.4 ± 0.1 and 1.2 ± 0.3 μg/mL, respectively. Reproducibility and intermediate precision were determined using a hydrolyzed sulfoethyl cellulose el sample and ranged between 0.2 and 8.8% for migration times and between 0.3 and 10.4% for peak area. The method was applied to the analysis of the degree of substitution of synthetic sulfoethyl cellulose el samples obtained by variation of the synthetic process and compared to data obtained by elemental analysis.

Cellulose p-toluenesulfonic acid esters (TosCell) with degree of substitution (DSTos) between 0.8 and 1.4 were converted with ethylene diamine or tris(2-aminoethyl)amine. In contrast to procedures published, the conversion was carried out without any solvent, i.e., the reagent (amines) was used as reaction medium yielding readily soluble products. Moreover, the absence of an additional solvent makes the recycling of both not-consumed amine and precipitant easy. Recycling experiments proofed the possibility of reusing the isolated ethylene diamine. The DS of 6-deoxy-6-(ω-aminoalkyl)amino groups is between 0.71 and 0.93, which is in accordance with the functionalization pattern of tosyl cellulose and the ability of amines to displace primary tosylate moieties only. Attention must be paid to the precipitant used for the workup procedure; 13C NMR measurements revealed a formation of imine structures in case of precipitation with acetone. Precipitation in 2-propanol did not lead to any side product. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43987.

This article provides detailed insight into the thermoresponsive gelation mechanism of industrially produced methylcellulose (MC), highlighting the importance of diblock structure with a hydrophobic sequence of 2,3,6-tri-O-methyl-glucopyranosyl units for this physicochemical property. We show herein, for the first time, that well-defined diblock MC self-assembles thermoresponsively into ribbonlike nanostructures in water. A cryogenic transmission electron microscopy (cryo-TEM) technique was used to detect the ribbonlike nanostructures formed by the diblock copolymers consisting of hydrophilic glucosyl or cellobiosyl and hydrophobic 2,3,6-tri-O-methyl-cellulosyl blocks, methyl β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-methyl-celluloside 1 (G-236MC, DP(n) = 10.7, DS = 2.65), and methyl β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-methyl-celluloside 2 (GG-236MC, DP(n) = 28.2, DS = 2.75). Rheological measurements revealed that the gel strength of a dispersion of GG-236MC (2, 2.0 wt %) in water at 70 °C was 3.0 times stronger than that of commercial MC SM-8000, although the molecular weight of GG-236MC (2) having M(w) = 8 × 10(3) g/mol was 50 times smaller than that of SM-8000 having M(w) = 4 × 10(5) g/mol. Cryo-TEM observation suggested that the hydrogel formation of the diblock copolymers could be attributed to the entanglement of ribbonlike nanostructures self-assembled by the diblock copolymers in water. The cryo-TEM micrograph of GG-236MC (2) at 5 °C showed rectangularly shaped nanostructures having a thickness from 11 to 24 nm, although G-236MC (1) at 20 °C showed no distinct self-assembled nanostructures. The ribbonlike nanostructures of GG-236MC (2) having a length ranging from 91 to 864 nm and a thickness from 8.5 to 27.1 nm were detected above 20 °C. Small-angle X-ray scattering measurements suggested that the ribbonlike nanostructures of GG-236MC (2) consisted of a bilayer structure with a width of ca. 40 nm. It was likely that GG-236MC (2) molecules were oriented perpendicularly to the long axis of the ribbonlike nanostructure. In addition, wide-angle X-ray scattering measurements revealed that GG-236MC (2) in its hydrogel formed the same crystalline regions as 2,3,6-tri-O-methylcellulose. The influence of the DP of diblock MC with a DS of around 2.7 on the gelation behavior will be discussed.

Non-naturally branched polysaccharides were prepared homogeneously by reaction of cellulose in N,N-dimethyl acetamide/LiCl and the ionic liquid 1-N-butyl-3-methylimidazolium chloride with 2,3,4,6-tetraacetyl-1-bromo-α-D-glucopyranoside in the presence of triethylamine as base. Degrees of substitution up to 0.58 were realized. The samples were soluble in dimethyl sulphoxide and water. NMR spectroscopy and methylation analysis revealed the formation of 1,2-orthoesters. The purity of the products regarding non-bonded sugar molecules was evidenced by advanced NMR techniques (DOSY- and T2 measurements). In contrast to the reaction in 1-N-butyl-3-methylimidazolium chloride, 1-N-ethyl-3- methylimidazolium acetate acts not only as solvent but also as reagent and leads to the formation of cellulose acetate instead of the desired product.

Isolation and thermal analysis of hydrogels from Plantago ovata (PO), Salvia aegyptiaca (SA), Ocimum basilicum (OB) and Mimosa pudica (MP) are reported. The hydrogel obtained from PO was modified by cross-linking, carboxymethylation and ethylation as a model to see the effect of modification on thermal behavior. Activation energy, enthalpy, entropy, free energy change, pre-exponential factor, comprehensive index of intrinsic thermal stability (ITS) were determined from the thermograms. The ITS values indicated good thermal stabilities of the hydrogels. Hydrogels isolated from SA, OB and MP did not show significant differences in their thermal behavior, whereas significant differences in thermal profiles of PO gel and its modified forms were observed. The modified gels exhibited improved thermal stability. Formation of water, 2-hydroxybutanedial, 3-hydroxypropanal and 2-furfuryl alcohol as degradation products was detected in the GC–MS analysis of some of the materials. The possible implications of these results are discussed.

This article describes a new synthesis strategy to prepare diblock copolymers as model compounds for industrially produced cellulose ethers exemplified with methylcellulose (MC). To elucidate a key structure for thermoreversible gelation of MC, five regioselectively methylated celluloses 1–5 (236, 23, 26, 3, and 6 MC), five corresponding methyl-β-D-glucopyranosyl-(1→4)-cellulosides 6–10, and five equiv methyl-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosyl-(1→4)-cellulosides 11–15 were synthesized for the first time via combination of the glycosyl trichloroacetimidate method and the acid-catalyzed methanolysis method. The structure of compounds 1–15 was confirmed by means of NMR spectroscopy and MALDI-TOF MS. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Cellulose derivatives bearing azide- and alkyne moieties were prepared by conversion of cellulose p -toluenesulphonic acid ester with sodium azide, on one hand, and propargylamine, on the other. The products obtained were carboxymethylated to yield water soluble multifunctional cellulose derivatives. Elemental analysis, FTIR- and NMR spectroscopy were applied to prove the structure of the polymers. SEC of the hydrogel components revealed values of the degree of polymerization (DP) between 43 and 200 that are acceptable values after this multi-step reaction starting from celluloses with DP 600. The copper(I)-catalyzed 1,3-dipolar cycloaddition reaction (Huisgen-reaction) was applied for the cross-linking. Gel formation occurred within 55 and 1600 s after mixing of the aqueous solutions of both components and copper(I) catalyst. The gelation time was found to depend on both the degree of functionalization and the amount of copper(I) catalyst. FTIR spectroscopy revealed incomplete conversion of the reactive sites. The gels contain up to 98.4% water. Freeze-drying led to spongy materials with a porous structure as visualised by SEM.

The homogeneous conversion of cellulose dissolved in N-methyl-2-pyrrolidone/LiCl and 1-N-butyl-3-methylimidazolium chloride with N-methyl-2-pyrrolidone, e-caprolactam, N-methyl-e-caprolactam, and N-methyl-2-piperidone in the presence of p-toluenesulphonic acid chloride was studied. Depending on the reaction conditions, novel cellulose esters with degree of substitution (DS) values ranging from 0.12 to 1.17 could be prepared. The structure of the amino group containing cellulose esters was elucidated by elemental analysis, FTIR- and NMR spectroscopy. NMR spectroscopy revealed an almost complete esterification of position 6 of the anhydroglucose unit at DS of 1. The conversion can be conducted between room temperature and 40 °C, while side-reactions became predominant at 60 °C. Starting with DS of 0.24, the samples were soluble both in water and dimethyl sulphoxide. The derivatives described are capable of forming polyelectrolyte complexes. The samples were stable at room temperature in aqueous solution at pH 2 and 7. Lower viscosities were found for samples with higher DS in aqueous solution at comparable molar mass.

Polysaccharide-based materials have gained nowadays a great importance in many fields of industry, e.g., in the pharmaceutical industry. Some characteristics of such compounds are their non-toxicity and the presence of a lower critical solution temperature (LCST) and/or an upper critical solution temperature (UCST). This work presents results on the synthesis and characterization of composites from hydroxypropyl cellulose (HPC) and polyacrylamide (PAAm). The ratio of HPC/PAAm was varied as well as the concentration of the crosslinker and the pH value of the reaction mixture. The compounds prepared were characterized by means of Fourier Transform Infrared spectroscopy (FTIR) and turbidity measurements. FTIR spectroscopy showed the presence of the main structural features of the precursors in the gels. The turbidity measurements of the gels in water showed the presence of a LCST in all samples. The LCST decreased when the quantity of HPC was increased in the gel and diminished also with increasing quantities of crosslinker and pH. The turbidity measurement showed the presence of an UCST when the concentration of the polymer was higher than 1 % (w/w). This phenomenon is caused by the presence of the PAAm, which acted as precipitant and influenced over the entropy of the system and provoked phase separation.

The objective of the present work is to analyze the different mesophases observed in a gel synthesized from hydroxypropyl cellulose (HPC) and polyacrylamide (PAAm) and its phase behavior in water. Hydroxypropyl cellulose is a material derived from cellulose it is non toxic and degradable. HPC is widely used in pharmaceutics, food additives, stabilizer, thickener, etc., HPC is approved by the FDA for use in the food industry. HPC has the characteristic that it forms liquid crystals, depending on the solvent and on the concentration of the polymer. In this work a lower critical solution temperature (LCST) and an upper critical solution temperature (UCST) were observed, the resulting gel showed anisotropic, nematic and cholesteric phases in water, the phase formed depended on the concentration of the polymer.

Spruce sulphite cellulose (number average degree of polymerization 620) dissolved in an aqueous solution of 8% (w/w) LiOH*H2O and 12% (w/w) urea was methylated with dimethyl sulphate (DMS). By varying the reaction temperature between 22 and 50 °C, the molar ratio between 9 and 15 mol DMS per mol anhydroglucose unit, and the reaction time from 4 to 24 h, methyl cellulose (MC) with degree of substitution (DS) values in the range of 1.07 and 1.59 was prepared. The chemical structure of MC was analysed by FTIR and 1H NMR spectroscopy. The turbidity (given in nephelometric turbidity units, NTU) of the aqueous solution of MC reached an optimum of 10 NTU for a product obtained with 12 mol DMS/mol AGU at 50 °C. GPC measurements revealed polymer degradation to a certain extent. The intrinsic viscosity and the Huggins constant k of the MC samples increased with increasing DS value. The MC samples possess k values higher than 0.8, indicating association of the polymer chain. The zero-shear viscosity decreased with increase of both temperature and the amount of methylation agent due to the depolymerization. During the heating/cooling cycle (20–90 °C) of the aqueous solutions of MC, it was observed that samples synthesized at 22 °C with DS values lower than 1.3 did not undergo phase separation in aqueous solution. Phase separation hysteresis with a precipitation temperature up to 80 °C was obtained for aqueous solutions of MC with DS values between 1.07 and 1.66 synthesized at higher temperatures. The functionalization pattern determined by GLC of the corresponding partially methylated glucitol acetates is close to randomness and comparable with those of commercial MC samples.

The synthesis of 3-O-propyl cellulose with degree of substitution (DS) ranging from 0.19 to 1.02 was carried out via 2,6-di-O-thexyldimethylsilyl cellulose. The products were characterized by means of one- and two-dimensional NMR spectroscopy after peracetylation. The dissolution behavior of 3-mono-O-propyl cellulose in water was studied and compared with propyl cellulose derivatives having different degree of substitution and distribution of functional groups. Depending on the DS, exceptionally low flocculation temperatures between 15 and 23 °C were found for 3-O-propyl celluloses.