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This study aimed to develop a polymeric matrix of polyamide-6 (P6) impregnated with trimetaphosphate (TMP) nanoparticles and silver nanoparticles (AgNPs), and to evaluate its antimicrobial activity, surface free energy, TMP and Ag+ release, and cytotoxicity for use as a support in dental tissue. The data were subjected to statistical analysis (p < 0.05). P6 can be incorporated into TMP without altering its properties. In the first three hours, Ag+ was released for all groups decorated with AgNPs, and for TMP, the release only occurred for the P6-TMP-5% and P6-TMP-10% groups. In the inhibition zones, the AgNPs showed activity against both microorganisms. The P6-TMP-2.5%-Ag and P6-TMP-5%-Ag groups with AgNPs showed a greater reduction in CFU for S. mutans. For C. albicans, all groups showed a reduction in CFU. The P6-TMP groups showed higher cell viability, regardless of time (p < 0.05). The developed P6 polymeric matrix impregnated with TMP and AgNPs demonstrated promising antimicrobial properties against the tested microorganisms, making it a potential material for applications in scaffolds in dental tissues.

In this study, sisal cellulose/magnetite-nanoparticle (Fe3O4 NPs; 0.5, 1.4, and 3.0 g L−1) hybrid films (denoted as FCFe0.5, FCFe1.4, and FCFe3.0, respectively) were prepared by casting, using the solvent system LiCl/DMAc. Sisal was chosen as a cellulose source because it is a fast-growing plant, in contrast to the long cycle of woody trees, and Brazil accounts for most of the sisal produced in the world. Fe3O4 NPs were chosen owing to their excellent properties (superparamagnetic behavior at room temperature, high chemical stability, and low toxicity). The synthesized magnetite NPs (coated with oleic acid and oleylamine to prevent agglomeration during synthesis) were spherical with an average diameter of 5.1 ± 0.5 nm (transmission electron microscopy analysis; TEM). X-ray diffraction analysis showed that the NPs were satisfactorily incorporated into the cellulose films (as confirmed by TEM) and that their presence favored the formation of cellulose crystalline domains. FCFe1.4 and FCFe3.0 exhibited higher tensile strengths (14.3 MPa and 12.1 MPa, respectively) than the neat cellulose film (9.9 MPa). The moduli of elasticity of FCFe0.5, FCFe1.4, and FCFe3.0 were 1650, 1500 MPa, and 780 MPa, respectively, lower than that of the cellulose film (1860 MPa), indicating that the incorporation of NPs in the cellulosic matrix decreased the films’ stiffness. Hybrid films exhibited high magnetizations at 300 K, i.e., 23.0 emu g−1 (FCFe0.5), 31.0 emu g−1 (FCFe1.4), and 37.0 emu g−1 (FCFe3.0), as well as no magnetic hysteresis and remanent magnetization (Mr) null, namely, a superparamagnetic behavior at room temperature. The results obtained suggest several applications of hybrid films based on cellulose and magnetite, such as biomedical applications, miniaturized electronic devices, and advanced catalysis. Keywords: Sisal cellulose, Magnetite nanoparticles, Magnetic hybrid films

Cellulose nanocrystals (CNC) exhibit remarkable properties such as being lightweight, renewability, nanoscale dimension, raw material availability, and a unique morphology. They have been widely used in film-forming composites, but the literature is scarce concerning bulky-composites (i.e., non-filmogenic). Microcrystalline cellulose (MCC) is widely available and has emerged as an important material for the reinforcement of composites. This investigation focuses on the preparation of non-filmogenic composites prepared from a polyurethane-type matrix, based on modified lignosulfonate and castor oil, reinforced with CNC or MCC, aiming to compare their reinforcing capacity. CNC was obtained through the acid hydrolysis of MCC. Sodium lignosulfonate was chemically modified using glutaraldehyde to increase its reactivity towards isocyanate groups in the synthesis of lignopolyurethane. The results show that adding CNC or MCC led to materials with improved impact strength, flexural properties, and storage modulus compared to pristine lignopolyurethane. With the exception of the flexural modulus, which was higher for the CNC-reinforced composite compared to the MCC-reinforced composite, all other properties were similar. The set of results indicates that CNC and MCC are promising for the reinforcement of polyurethane-type matrices. Bulky materials with good properties and prepared from high renewable raw material contents were obtained, meeting current expectations concerning sustainable development.

Composites based on a thermoset phenolic matrix and jute fibers were prepared and characterized. The fibers were alternatively treated with ionized air or aqueous alkaline solution (mercerization) with the aim of introducing changes in the morphology, dispersive component of surface free energy, γS D (estimated by Inverse Gas Chromatography, IGC) and the acid/base character of their surfaces, shown by their ANs/DNs ratio (estimated by IGC), and their degree of crystallinity. The final objective was to investigate the influence of these modifications on the adhesion at the jute fiber/phenolic matrix interface in the composites. The untreated jute fiber showed 50% crystallinity, γS D=18 mJ m- 2 and ANs/DNs= 0.9 (amphoteric surface), tensile strength = 460 MPa and maximum elongation = 0.7%, while the respective composite had an impact strength of 72.6 J m- 1. The treatments positively modified the fibers and the adhesion at the interface was better in the composites reinforced with treated fibers than with untreated fibers. The best set of results was exhibited by the fiber treated with 10% NaOH [46% crystallinity, γS D = 26 J m- 2 (phenolic matrix γS D = 32 J m- 2), ANs/DNs = 1.8 (surface predominantly acidic, similar to phenolic matrix, ANs/DNs = 1.4), tensile strength approximately 900 MPa, maximum elongation = 2%, impact strength of respective composite approximately 95 J m- 1)]. The fibers treated for 5 h with ionized air exhibited favorable properties [(45% crystallinity, γS D = 27 J m- 2, ANs/DNs = 2.1 (acidic surface)] for further use as reinforcement of a phenolic matrix, but their partial degradation during the treatment decreased their tensile properties (395 MPa and 0.5% for tensile strength and maximum elongation, respectively) and their action as reinforcement (impact strength of the respective composite approximately 73 J m- 1).

Neste trabalho, foram utilizadas fibras de curauá como reforço de matriz termoplástica de biopolietileno de alta densidade. O polietileno foi obtido por polimerização de eteno, gerado do etanol de cana de açúcar. Este polímero é também chamado de biopolietileno (BPEAD), por ser preparado a partir de material oriundo de fonte natural. Desta forma, pretendeu-se contribuir para desenvolver materiais que, dentre outras propriedades, causem menor emissão de CO2 para a atmosfera na sua produção, utilização e substituição, comparativamente a outros materiais. Adicionalmente, polibutadieno líquido hidroxilado (PBHL) foi acrescentado à formulação do compósito, visando a um aumento na resistência à propagação da trinca durante impacto. Os compósitos e as fibras foram caracterizados por várias técnicas, tais como microscopia eletrônica de varredura (MEV), Calorimetria Exploratória Diferencial (DSC), Termogravimetria (TG), além da caracterização dos compósitos quanto à Análise Térmica Dinâmico-Mecânica (DMTA), propriedades mecânicas (impacto e flexão) e absorção de água. A presença das fibras de curauá diminuiu algumas propriedades do BPEAD, como resistência ao impacto. A análise de DMTA mostrou que as fibras geram material mais rígido. Pode-se considerar que a introdução de PBHL na formulação do material foi eficiente, levando a uma resistência ao impacto do compósito BPEAD/PBHL/Fibra maior do que a do compósito BPEAD/Fibra.In this work, curaua fibers were used in the reinforcement of a high-density (HDPE) thermoplastic matrix. The polyethylene used was obtained by polymerization of ethene produced from sugarcane ethanol. This polymer, also called high-density biopolyethylene (HDBPE), was prepared from a natural source material. The aim was to contribute to developing materials which could lead to smaller release of CO2 into the atmosphere in comparison to other materials. Additionally, liquid hydroxylatedpolybutadiene (LHPB) was added to the composite formulation, aiming at improving resistance to crack spreading during impact. The fibers and their composites were characterized by several techniques, such as scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetry (TG). The composites were also characterized by dynamic mechanical thermal analysis (DMTA), mechanical properties (flexural and impact strength), and water absorption. The presence of curaua fibers reduced some of the properties of HDBPE, such as flexural and impact strength. DMTA indicated a more rigid material with the fibers incorporated. The addition of LHPB to the formulation was efficient, leading to greater impact strength for the HDBPE/LHPB/Fiber composite, as compared to the HDBPE/Fiber composite.

Cellulose fibers obtained from the textile industry (lyocell) were investigated as a potential reinforcement for thermoset phenolic matrices, to improve their mechanical properties. Textile cotton fibers were also considered. The fibers were characterized in terms of their chemical composition and analyzed using TGA, SEM, and X-ray. The thermoset (non-reinforced) and composites (phenolic matrices reinforced with randomly dispersed fibers) were characterized using TG, DSC, SEM, DMTA, the Izod impact strength test, and water absorption capacity analysis. The composites that were reinforced with lyocell fibers exhibited impact strengths of nearly 240 Jm-1, whereas those reinforced with cotton fibers exhibited impact strengths of up to 773 Jm-1. In addition to the aspect ratio, the higher crystallinity of cotton fibers compared to lyocell likely plays a role in the impact strength of the composite reinforced by the fibers. The SEM images showed that the porosity of the textile fibers allowed good bulk diffusion of the phenolic resin, which, in turn, led to both good adhesion of fiber to matrix and fewer microvoids at the interface.

Cellulose acetates with different degrees of substitution (DS, from 0.6 to 1.9) were prepared from previously mercerized linter cellulose, in a homogeneous medium, using N,N-dimethylacetamide/lithium chloride as a solvent system. The influence of different degrees of substitution on the properties of cellulose acetates was investigated using thermogravimetric analyses (TGA). Quantitative methods were applied to the thermogravimetric curves in order to determine the apparent activation energy (Ea) related to the thermal decomposition of untreated and mercerized celluloses and cellulose acetates. Ea values were calculated using Broido's method and considering dynamic conditions. Ea values of 158 and 187 kJ mol-1 were obtained for untreated and mercerized cellulose, respectively. A previous study showed that C6OH is the most reactive site for acetylation, probably due to the steric hindrance of C2 and C3. The C6OH takes part in the first step of cellulose decomposition, leading to the formation of levoglucosan and, when it is changed to C6OCOCH3, the results indicate that the mechanism of thermal decomposition changes to one with a lower Ea. A linear correlation between Ea and the DS of the acetates prepared in the present work was identified.Acetatos de celulose com graus de substituição, GS, variando entre 0,6 e 1,9, foram preparados previamente a partir de celulose de linter mercerizado, em meio homogêneo, usando N,N-dimetilacetamida/cloreto de lítio como sistema de solvente. A influência de diferentes graus de substituição nas propriedades dos acetatos de celulose foi investigada usando a análise termogravimétrica (TGA). Métodos quantitativos foram aplicados nas curvas termogravimétricas obtidas a fim de determinar a energia de ativação aparente (Ea) relacionado à decomposição térmica de celulose não-tratada e mercerizada e acetatos de celulose. Valores de Ea foram calculados usando o método de Broido e considerando condições dinâmicas. Valores de Ea de 158 e 187 kJ mol-1 foram obtidos para a celulose não-tratada e mercerizada, respectivamente. Em trabalho anterior verificou-se que o C6OH é o sítio mais reativo na acetilação, provavelmente devido ao impedimento estérico de C2 e C3. O C6OH participa da primeira etapa de decomposição da celulose, levando à formação de levoglucosana e, quando se tem a substituição para C6OCOCH3, o resultado indica que o mecanismo de decomposição térmica muda para um com Ea menor. Uma correlação linear entre Ea e o GS dos acetatos preparados no presente trabalho foi identificada.

The aim of this study was to evaluate: (i) the absorption of photo-initiators and emission spectra of light curing units (LCUs); and (ii) the degree of conversion (DC) of experimental composites formulated with different photo-initiators when activated by different LCUs. Blends of BisGMA, UDMA, BisEMA and TEGDMA with camphorquinone (CQ) and/ or 1-phenyl-1,2-propanedione (PPD) were prepared. Dimethylaminoethyl methacrylate (DMAEMA) was used as co-initiator. Each mixture was loaded with 65 wt% of silanated filler particles. One quartz-tungsten-halogen - QTH (XL 2500, 3M/ESPE) and two lightemitting diode (LED) LCUs (UltraBlue IS, DMC and UltraLume LED 5, Ultradent) were used for activation procedures. Irradiance (mW/cm²) was calculated by the ratio of the output power by the area of the tip, and spectral distribution with a spectrometer (USB 2000). The absorption curve of each photo-initiator was determined using a spectrophotometer (Varian Cary 5G). DC was assessed by Fourier transformed infrared spectroscopy. Data were submitted to two-way ANOVA and Tukey's test (5%). No significant difference was found for DC values when using LED LCUs regardless of the photo-initiator type. However, PPD showed significantly lower DC values than composites with CQ when irradiated with QTH. PPD produced DC values similar to those of CQ, but it was dependent on the LCU type.

Glioxal pode ser obtido a partir de biomassa (como da oxidação de lipídeos) e não é tóxico ou volátil, tendo sido por isso utilizado no presente trabalho como substituto de formaldeído na preparação de resina fenólica do tipo novolaca, sendo usado como catalisador o ácido oxálico, que também pode ser obtido de fontes renováveis. A resina glioxal-fenol foi utilizada na preparação de compósitos reforçados com celulose microcristalina (CM, 30, 50 e 70% em massa), uma celulose com elevada área superficial. As imagens de microscopia eletrônica de varredura (MEV) das superfícies fraturadas demonstraram que os compósitos apresentaram boa interface reforço/matriz, consequência da elevada área superficial da CM e presença de grupos polares (hidroxilas) tanto na matriz como na celulose, o que permitiu a formação de ligações hidrogênio, favorecendo a compatibilidade entre ambas. A análise térmica dinâmico-mecânica (DMTA) demonstrou que todos os compósitos apresentaram elevado módulo de armazenamento à temperatura ambiente. Além disso, o compósito reforçado com 30% de CM apresentou baixa absorção de água, comparável à do termorrígido fenólico, que é utilizado em escala industrial. Os resultados demonstraram que compósitos com boas propriedades podem ser preparados usando elevada proporção de materiais obtidos de biomassa.Glyoxal, which can be obtained from biomass (as by lipids oxidation), is non-toxic and non-volatile. It was used as a substitute of formaldehyde, which does not have these properties, in the synthesis of a novolac-type phenolic resin, using oxalic acid as a catalyst, which can also be obtained from renewable sources. The glyoxal-phenol resin was used in the preparation of composites reinforced with microcrystalline cellulose (MCC 30, 50, and 70% w/w). Scanning electron microscopy (SEM) images of the fractured surfaces showed that the composites presented a good reinforcement/matrix interface. This can be attributed to the high surface area of the MCC and also to the presence of polar groups (hydroxyl) in both cellulose and matrix, which allowed the formation of hydrogen bonds, leading to a good adhesion between the components present at the interface. Dynamic mechanical thermoanalysis (DMTA) showed that all of the obtained composites have high storage modulus at room temperature. Moreover, the composite reinforced with 30% of MCC showed the lowest water absorption, almost the same as that of the phenolic thermoset, which is used in industrial applications. The results showed that composites with good properties can be prepared using high proportions of materials obtained from biomass.

The purpose of this study was to evaluate the degree of conversion (DC) of the Z250 composite, using six photo-activation methods, two storage periods and two preparation techniques of the FTIR specimens (n = 3). For the KBr pellet technique, the composite was placed into a metallic mold and photo-activated as follows: continuous light, exponential light, intermittent light, stepped light, PAC and LED. The measurements were made after 24 h and 20 days. For the resin film technique, approximately 0.07 g of the composite was pressed between two polyester strips, photo-activated as above described and analyzed. The DC was calculated by the standard technique and submitted to ANOVA and Tukey's test (alpha = 5%). Independently of the storage period and specimen preparation technique, there were no significant differences among photo-activation methods. No statistical difference was observed between the time periods used. The specimens analyzed under the KBr pellet technique presented higher DC values than those analyzed by the resin film technique.

Pré-polímeros fenólicos e lignofenólicos (substituição de 40% em massa de fenol por lignina, extraída do bagaço de cana) foram sintetizados para preparar compósitos com matrizes termofixas, usando bagaço de cana-de-açúcar como agente de reforço. Este material lignocelulósico foi modificado por métodos químicos e/ou físicos (tratamento com álcali, esterificação, ar ionizado). O bagaço de cana promoveu pequeno aumento na resistência ao impacto das matrizes fenólica e lignofenólica. Os métodos de tratamento de superfície melhoraram a dispersão das fibras na matriz assim como a adesão entre ambas as resinas, fenólica e lignofenólica, e as fibras lignocelulósicas. Apenas os compósitos tratados com ar ionizado mostraram melhores resultados de resistência ao impacto. Em relação à absorção de água, foi observado que os compósitos fenólicos reforçados com fibras tratadas com 8 % NaOH apresentaram uma menor absorção de água. Quanto aos compósitos lignocelulósicos, os reforçados com fibras esterificadas apresentaram uma menor absorção de água.

Celulose de linter foi acetilada, visando obter acetatos de celulose com diferentes Graus de Substituição (GS) em meio homogêneo, usando cloreto de lítio/N,N-dimetilacetamida (LiCl/DMAc) como sistema de solvente, e anidrido acético como reagente acetilante. A agregação entre cadeias de celulose ou acetatos de celulose (GS 0,8, 1,5 e 2,0) em solução foi avaliada através de medidas viscosimétricas. Os resultados mostraram que a formação de agregados no sistema de solvente utilizado (LiCl/DMAc) é diferente para celulose e acetatos, e dependente da temperatura e do GS, no caso dos acetatos. Este trabalho corresponde à primeira etapa de um estudo em que se pretende preparar filmes de acetatos, assim como de acetatos reforçados com celulose, diretamente a partir de soluções destes em LiCl/DMAc. Os resultados apresentados permitem uma escolha melhor embasada do intervalo de concentração mais adequado para preparação de filmes, a partir de soluções de acetatos e celulose nesse sistema de solvente.Linters cellulose was acetylated to obtain cellulose acetates with different degrees of substitution (DS) in homogeneous medium, using lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) as solvent system, and acetic anhydride as acetylating agent. The aggregation among chains of cellulose or cellulose acetates (DS 0.8, 1.5 and 2.0) in solution was studied through viscometric measurements. The results showed that aggregation in LiCl/DMAc is different for cellulose and acetates, and depends on the temperature and DS in the case of acetates. This study corresponds to the first step of a project, which aims at to prepare cellulose acetates films, as well as acetates films reinforced with cellulose, by casting directly from these solutions in LiCl/DMAc. The results presented here allow for an optimized choice of concentration range for preparing films from LiCl/DMAc solutions of acetates and cellulose.

Neste trabalho, pré-polímeros do tipo fenólico ( resóis ) e lignina - fenol ( 40% w/w ) foram sintetizados e usados na preparação de matrizes em compósitos reforçados com diversas fibras vegetais : sisal, curaua e bagaço de cana-de açúcar, sendo as fibras previamente extraídas com cicloexano/etanol. Os compósitos reforçados com sisal apresentaram um aumento significativo na resistência ao impacto, quando comparados com a matriz termofixa. As fibras de curaua foram submetidas a um tratamento adicional com NaOH 10%, tendo os respectivos compósitos apresentado também resistência ao impacto superior ao da matriz fenólica não reforçada., enquanto que os compósitos reforçados com bagaço de cana de açúcar apresentaram pequena alteração nesta propriedade.

Neste trabalho, a lignina extraída pelo processo organossolve do bagaço de cana-de-açúcar substituiu parcialmente fenol (40% em massa) em matrizes termofixas reforçadas com fibras curtas de bagaço de cana-de-açúcar (30, 40, 50, 60 e 70%, v/v). Os compósitos obtidos foram caracterizados por TG, DSC, DMTA, Resistência ao Impacto Charpy, Dureza Shore D. Os resultados obtidos mostraram ser viável a substituição de fenol por lignina em matrizes fenólicas. No entanto, para que se obtenha compósitos com propriedades compatíveis com às exigidas para aplicações industriais, modificações devem ser feitas: modificação de fibras por meio de reações químicas, diversificação do comprimento das fibras vegetais, realização de etapas de cura em temperaturas superiores as consideradas no presente trabalho.In this work the performance of thermoset phenolic/sugar cane bagasse composites were ascertained as a function of fiber content and matrix modification. The matrix was modified by using lignin, extracted from sugar cane bagasse, as a partial (40% wt) phenol substitute. The thermoset polymer matrices and related composites were compression moulded and the products were characterized by TG, DSC, DMTA, Impact Strength, Shore D Hardness. Our results indicate that phenol can be substituted by lignin in the synthesis of phenolic resins. However, further work is necessary if one is to obtain composites complying with the performance demanded for industrial applications. In this case, chemical modification of the fibers, varying lengths of the vegetables fibers and cure steps at higher temperatures than the ones considered here must be performed.

A lignina extraída do bagaço de cana de açúcar pode substituir parcialmente o fenol na preparação de resinas fenólicas. Este trabalho aborda a aplicação de pré-polímero resólico, sendo que o fenol foi parcialmente substituído por lignina (25%, massa lignina/massa fenol ), visando a obtenção de material com características de plástico celular. No presente trabalho descreve-se a caracterização das espumas obtidas por microscopia eletrônica de varredura, conteúdo de células fechadas, densidade aparente, resistência à compressão e dureza. A espuma lignina-fenol-formaldeído apresentou propriedades mecânicas consideravelmente superiores àquelas da espuma fenólica convencional, caracterizando-se como uma espuma estrutural, com características de isolante térmico.Lignin can be recovered from sugar cane bagasse, which is largely available in Brazil, as a residue from sugar mills. This work presents a new application for lignin-phenol formaldehyde polymers in cellular materials. The foams obtained were characterized by scanning electron microscopy, open cell content, apparent density, compressive strength, hardness. The lignin-phenol-formaldehyde foam presents a thermal insulating characteristics combined with remarkable mechanical properties, which allows its application as structural-thermal insulation foam

RESUMO: Polpas etanol/água de medula de bagaço de cana de açúcar foram empregadas para a obtenção de carbóxi-metil-celulose insolúvel, aplicável como material absorvente. Tipicamente, a reação de carbóxi-metilação da polpa branqueada foi realizada em suspensão de isopropanol/água (1:8 / m:m) a 80 ºC por 4 horas, empregando-se relação molar 1 / 5,4 / 8,8 de celulose / NaOH / ClAcOH. O material com melhores características corresponde a um produto muito pouco solúvel (S W < 2%), com propriedades absorventes superiores às da polpa de partida.ABSTRACT: Ethanol/water pulp of pith from sugar cane bagasse was used for the obtention of insoluble carboxymethylcellulose applicable as absorbent material. Typically the carboxymethylation reaction of the bleached pulp was carried out at 80 °C for 4 hours in isopropanol/water suspension 1:8 (w/w) employing a 1.0 / 5.4 / 8.8 cellulose / NaOH / ClAcOH molar ratio. The material with the best absorbent characteristics corresponds to a very insoluble product (S W < 2%) possessing better absorbent properties than the pulp of pith used for its obtention.

The question posed in the title has been addressed by studying the swelling of celluloses at 20 °C by twenty protic solvents, including water; linear- and branched-chain aliphatic alcohols; unsaturated aliphatic alcohols, and alkoxyalcohols. The biopolymers investigated included microcrystalline cellulose, MC, native and never-dried mercerized cotton cellulose, cotton and M-cotton, and native and never-dried mercerized eucalyptus cellulose, eucalyptus and M-eucalyptus, respectively. In most cases, better correlations with the physico-chemical properties of the solvents were obtained when the swelling was expressed as number of moles of solvent/anhydroglucose unit, nSw, rather than as % increase in sample weight. The descriptors employed in these correlations included, where available, Hildebrand’s solubility parameters, Gutmann’s acceptor and donor numbers, solvent molar volume, VS, as well as solvatochromic parameters. The latter, employed for the first time for correlating the swelling of biopolymers, included empirical solvent polarity, ET(30), solvent “acidity”, αS, “basicity”, βS, and dipolarity/polarizability, πS*, respectively. Small regression coefficients and large sums of the squares of the residues were obtained when values of nSw were correlated with two solvent parameters. Much better correlations were obtained with three solvent parameters. The most statistically significant descriptor in the correlation equation depends on the cellulose, being πS* for MC, cotton, and eucalyptus, and VS for M-cotton and M-eucalyptus. The best correlations were obtained with the same set of four parameters for all celluloses, namely, solvent pKa (or αS) βS, πS*, and VS, respectively. These results indicate that the supra-molecular structure of the biopolymer, in particular the average sizes of crystallites and micro-pores, and the presence of its chains in parallel (cellulose I) or anti-parallel (cellulose II) arrangements control its swelling. At least for the present biopolymer/solvent systems, use of solvatochromic parameters is a superior alternative to Hildebrand’s solubility parameters and/or Gutmann’s acceptor and donor numbers. The relevance of these results to the accessibility of the hydroxyl groups of cellulose, hence to its reactivity, is briefly discussed. [ABSTRACT FROM AUTHOR]

AbstractSteady-state fluorescence emission spectra of various celluloses were measured at an excitation wavelength of 320 nm. Various spectra recorded in the solid state were compared: (1) ECF bleached papers made of hardwood, the anhydroglucose units of which were chemically modified at C1and C6or C2and C3positions with carboxylic groups; (2) microcrystalline cellulose; (3) cotton linters; and (4) delignified sisal fibers (mercerized or not). Fluorescence emission was quite independent of the carboxylic acid content and average molecular weight (determined by viscosimetry) of the cellulose polymers. Microcrystalline cellulose (Avicel), cotton linters, and mercerized delignified sisal cellulose were acetylated in homogeneous medium (DMAc/LiCl as solvent system) to obtain soluble polymers in dichloromethane for comparison of spectra recorded in the solid and liquid states. Fluorescence of cellulose acetates in solution (CH2Cl2) and in the solid state was compared under similar experimental conditions to non-esterified celluloses in the solid state. The importance of the solid state for fluorescence emission could be demonstrated. Fluorophores are present in minute amounts in the polymer and their favorable energy transfer for excitation in the solid state likely enhances fluorescence emission. Among numerous fluorophores, dityrosine appeared to be a good candidate for fluorescence because it displayed emission in the fluorescence range of cellulose. Dityrosine is an amino acid involved in the lignification of non-woody plants. Mercerized sisal impregnated with tyrosine in the presence of peroxidase and hydrogen peroxide did not show enhanced emission, in contrast to para-hydroxycinnamic acid (coumaric acid), which is also involved in the lignification process at least for non-woody plants. The origin of cellulose fluorescence remains uncertain and appears to have several origins. This study clearly underlines the importance of the solid state for enhancing fluorophore emission. [ABSTRACT FROM AUTHOR]