Investigation of the supramolecular structure of never dried bacterial cellulose

Supramolecular structure of initially wet bacterial cellulose of Acetobacter xylinum has been investigated by X-ray scattering including synchrotron radiation, transmission electron microscopy, and ¹³C-CP/MAS-NMR-spectroscopy. As a result a model is given of never dried swollen microfibrillar ribbons consisting of 5 to 12 waterfree I_α-crystalline subunits with a cross-section of about 7 nm × 13 nm and of water solvating the subunits. Lateral aggregation of these crystalline units was found along the smaller (110)-lattice planes with a layer of water between adjacent crystallites. The NMR-spectrum of wet bacterial cellulose exhibits an additional C-1 line component indicating cellulose-water interactions. During drying lateral dimensions of the microfibrillar ribbons, crystallite sizes, as well as the overall crystalline order decrease, whereas the Iα/Iβ-ratio of about 80/20 remains approximately unchanged. Conclusions were drawn with regard to the early states of structure formation of bacterial cellulose.     

Microfibril diameter in celery collenchyma cellulose: X-ray scattering and NMR evidence

Cellulose isolated from celery collenchyma is typical of the low-crystallinity celluloses that can be isolated from primary cell-walls of higher plants, except that it is oriented with high uniformity. The diameter of the microfibrils of celery collenchyma cellulose was estimated by three separate approaches: ¹³C NMR measurement of the ratio of surface to interior chains; estimation of the dimensions of the crystalline lattice from wide angle X-ray scattering (WAXS) measurements using the Scherrer equation; and the observation that microfibrils of this form of cellulose have the unusual property of packing into an irregular array from which small angle X-ray scattering (SAXS) shows features of both form and interference functions. The interference function contributing to the SAXS pattern implied a mean microfibril centre-to-centre distance of 3.6 nm, providing an upper limit for the diameter. However modelling of the scattering pattern from an irregular array of microfibrils showed that the observed scattering curve could be matched at a range of diameters down to 2.4 nm, with the intervening space more or less sparsely occupied by hemicellulose chains. The lateral extent of the crystalline lattice normal to the 200 plane was estimated as a minimum of 2.4 nm by WAXS through the Scherrer equation, and a diameter of 2.6 nm was implied by the surface: volume ratio determined by ¹³C NMR. The WAXS and NMR measurements both depended on the assumption that the surface chains were positioned within an extension of the crystalline lattice. The reliability of this assumption is uncertain. If the surface chains deviated from the lattice, both the WAXS and the NMR data would imply larger microfibril diameters within the range consistent with the SAXS pattern. The evidence presented is therefore all consistent with microfibril diameters from about 2.4 to 3.6 nm, larger than has previously been suggested for primary-wall cellulose. Some degree of aggregation may have occurred during the isolation of the cellulose, but the larger microfibril diameters within the range proposed are a consequence of the novel interpretation of the experimental data from WAXS and NMR and are consistent with previously published data if these are similarly interpreted.     

Structure and spacing of cellulose microfibrils in woody cell walls of dicots

The structure of cellulose microfibrils in situ in wood from the dicotyledonous (hardwood) species cherry and birch, and the vascular tissue from sunflower stems, was examined by wide-angle X-ray and neutron scattering (WAXS and WANS) and small-angle neutron scattering (SANS). Deuteration of accessible cellulose chains followed by WANS showed that these chains were packed at similar spacings to crystalline cellulose, consistent with their inclusion in the microfibril dimensions and with a location at the surface of the microfibrils. Using the Scherrer equation and correcting for considerable lateral disorder, the microfibril dimensions of cherry, birch and sunflower microfibrils perpendicular to the [200] crystal plane were estimated as 3.0, 3.4 and 3.3 nm respectively. The lateral dimensions in other directions were more difficult to correct for disorder but appeared to be 3 nm or less. However for cherry and sunflower, the microfibril spacing estimated by SANS was about 4 nm and was insensitive to the presence of moisture. If the microfibril width was 3 nm as estimated by WAXS, the SANS spacing suggests that a non-cellulosic polymer segment might in places separate the aggregated cellulose microfibrils.     

Carbon-13 solid state NMR investigation and modeling of the morphological reorganization in regenerated cellulose fibres induced by controlled acid hydrolysis

CPMAS carbon-13 NMR has been used to follow structural changes affecting regenerated cellulose fibres during hydrolysis by mineral acids. The C4 envelope of regenerated cellulose was deconvoluted into separate peaks, for ordered (crystal), part-ordered (surface) and disordered (non-crystal) polymer, which allowed calculation of average crystal lateral sizes, in good agreement with WAXD data. A geometrical model has been used to describe recrystallisation at lateral crystal faces, occurring within a disordered boundary surrounding the crystal interior. A one-dimensional relaxation-diffusion model has also been constructed, appropriate to the spinodal structure of lyocell. This has provided estimates of proton T_1ρ relaxation times for pure crystalline (cellulose II) and non-crystalline cellulose, around 24 and 4.5 ms, respectively, at a 45 kHz B₁ field. From the model, crystalline and non-crystalline regions in lyocell are estimated to each be around 2.5 nm thickness for a material of 50% crystallinity, consistent with the 2–3 nm dimensions derived from C4 peak devonvolution.     

Size,shape, orientation and crystallinity of cellulose I<Subscript>β</Subscript> by X-ray powder diffraction using a free spreadsheet program

X-ray powder diffraction is one of the most commonly used methods in cellulose science. This technique is used to identify the cellulose allomorphs, their crystallinity, and the size of their crystallites. In this paper, a novel model is introduced that implicitly takes into account the shape and size of cellulose I_β crystallites in the interpretation of powder diffractograms. Because of the limited amount of data in cellulose powder patterns, this model focuses on a small number of adjustable parameters. The method hypothesizes that cellulose I_β crystallites are straight crystalline rods with superelliptical cross-sections. This superellipse is a parametric curve that can, for example, describe various crystallite shapes as rectangles or ellipses. Additionally, preferred orientation along the (0 0 1) crystallographic planes can be modelled using the March–Dollase approach. The simulated background has a semi-empirical form. An initial model comprised cellulose I_β crystallites and the amorphous background. A second model comprised a biphasic distribution of crystallites and the same amorphous background. In this second model, large cellulose I_β crystallites coexisted with more slender crystallites, usually less than 20 Å in lateral size. Cellulose IV_I nanocrystals were selected as a modeling construct to represent these small and distorted forms of native cellulose. Both models produced simulations in excellent agreement with the experimental measurements.     

The features of nitric acid ‘mercerization’ of cellulose

Transformation of native cellulose species into cellulose-II polymorph through the additive Knecht compound formed under the action of 68.5% nitric acid has been studied. Probable causes of peculiar temperature effects in the course of phase transformations taking place in cellulose of various origin, crystallite dispersity, or morphologic structure are discussed. The processes of hydrolytic destruction and esterification of starting materials during their mercerization by this non-traditional agent at 20 °C and 0 °C are quantitatively characterized. In the case of mercerization of wood microcrystalline cellulose at 20 °C a decrystallizing effect due to side reactions of partial nitration is noted.     

Crystalline transformation of native cellulose from cellulose I to cellulose ID polymorph by a ball-milling method with a specific amount of water

We have demonstrated for the first time that a mechano-chemical treatment of native cellulose with a specific amount of water (30 wt%) present ID the cellulose solid state caused the crystalline transformation from cellulose I into cellulose ID polymorph. X-ray diffractometry was used to show that the extent of transformation into cellulose ID increased with milling time. This specific phenomenon can be explained by considering the chain mobility ID the cellulose–water system, because ₁ ^1H measurement shows that cellulose molecules are most mobile when the water content ID around 30 wt%, and thus are favorable for molecular rearrangement under external forces.     

In situ crystallization of bacterial cellulose II. Influences of different polymeric additives on the formation of celluloses Iα and Iβ at the early stage of incubation

Effects of polymeric additives with different degrees of polymerization (DP) or substitution (DS) on the crystallization of celluloses I and I have been examined at an early stage of the incubation of Acetobactor xylinum by using newly developed FT-IR spectroscopy. It was found that the mass fraction of cellulose I is greatly decreased with increasing concentrations of carboxymethyl cellulose sodium salt (CMC) or xyloglucan (XG) in the incubation medium. Such a decrease in the mass fraction of cellulose I, which corresponds to the enhanced crystallization of cellulose I, is more prominent for CMC or XG with lower DPs, but the additives with too low DPs are not so effective probably due to higher solubility and the lower adhesion on the surface of microfibrils. Moreover, the mass fractions of celluloses I and I are highly correlated with the crystallite size of microfibrils, indicating that I is crystallized in larger-size microfibrils while I is produced in smaller-size microfibrils. On the basis of these experimental results, the mechanism of the crystallization of celluloses I and I is discussed in the Acetobactor xylinum system.     

Neptunium(V) Carbamide Complexes. The structure of [NpO2(HCOO){OC(NH2)2}3]

A new complex of Np(V) [NpO₂(HCOO){OC(NH₂)₂}₃] (I) was synthesized and its crystal structure was determined: a = 6.674(1) Å, b = 13.164(2) Å, c = 7.020(1) Å, = 101.35(1)°, space group P2₁, Z = 2, V = 604.7(2) ų, R = 0.048, wR(F ²) = 0.128. The structure consists of infinite chains of [NpO₂(HCOO){OC(NH₂)₂}₃]. The coordination polyhedron of the Np atom is a pentagonal bipyramid with the O atoms of three carbamide molecules and two formate ions in the equatorial plane. The absorption spectra were measured in IR and near-IR regions for compound I and for the [NpO₂Cl{OC(NH₂)₂}₄] complex, whose structure was reported in the previous publication.     

Watching Nanoparticles Form: An In Situ (Small‐/Wide‐Angle X‐ray Scattering/Total Scattering) Study of the Growth of Yttria‐Stabilised Zirconia in Supercritical Fluids

Understanding nanoparticle‐formation reactions requires multi‐technique in situ characterisation, since no single characterisation technique provides adequate information. Here, the first combined small‐angle X‐ray scattering (SAXS)/wide‐angle X‐ray scattering (WAXS)/total‐scattering study of nanoparticle formation is presented. We report on the formation and growth of yttria‐stabilised zirconia (YSZ) under the extreme conditions of supercritical methanol for particles with Y₂O₃ equivalent molar fractions of 0, 4, 8, 12 and 25 %. Simultaneous in situ SAXS and WAXS reveals a quick formation (seconds) of sub‐nanometre amorphous material forming larger agglomerates with subsequent slow crystallisation (minutes) into nanocrystallites. The amount of yttria dopant is shown to strongly affect the crystallite size and unit‐cell dimensions. At yttria‐doping levels larger than 8 %, which is known to be the stoichiometry with maximum ionic conductivity, the strain on the crystal lattice is significantly increased. Time‐resolved nanoparticle size distributions are calculated based on whole‐powder‐pattern modelling of the WAXS data, which reveals that concurrent with increasing average particle sizes, a broadening of the particle‐size distributions occur. In situ total scattering provides structural insight into the sub‐nanometre amorphous phase prior to crystallite growth, and the data reveal an atomic rearrangement from six‐coordinated zirconium atoms in the initial amorphous clusters to eight‐coordinated zirconia atoms in stable crystallites. Representative samples prepared ex situ and investigated by transmission electron microscopy confirm a transformation from an amorphous material to crystalline nanoparticles upon increased synthesis duration.     

Crystallite sizes and paracrystalline lattice distortions in drawn hard elastic polypropylene

Summary The paracrystalline lattice distortions and the mosaic crystallite sizeD ₀₀₁ are constant at all draw ratios ( =1 ... 2,3) of a hard elastic polypropylene foil. The lateral crystallite sizes decrease sharply (but not much) at a small draw ratio and slow to higher .

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Zusammenfassung Beim Verstrecken einer hartelastischen Polypropylen-Folie (Verstreckgrade =1 ... 2,3) bleiben die parakristallinen Gitterstörungen und die MosaikkristallitgrößeD ₀₀₁ konstant. Die lateralen Kristallitgrößen nehmen bei kleinem A steil, aber wenig, ab und verringern sich dann langsam weiter mit wachsendem .

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With 2 figures     

In Situ Crystallization of Bacterial Cellulose III. Influences of Different Polymeric Additives on the Formation of Microfibrils as Revealed by Transmission Electron Microscopy

Effects of polymer additives on the formation of microfibrils of bacterial cellulose have been examined by transmission electron microscopy. Among additives with different degrees of polymerization (DP) or substitution (DS), carboxymethyl cellulose sodium salt (CMC) with DP = 80 and DS = 0.57 is the most effective in producing separate, smaller-size microfibrils. By increasing the concentration of this CMC from 0.1 to 1.5%, the percentage of microfibrils measuring 3–7 nm wide is increased and levels off at around 1.0%. Other polymer additives such as xyloglucan are less effective than CMC in producing microfibrils with smaller sizes and the resulting microfibrils still tend to aggregate. The number of charged substituents and the molecular weight seem to be important factors in the production of highly separate smaller-size microfibrils. The reduction in average microfibril size is well correlated to the decrease in mass fraction of cellulose I in bacterial cellulose crystals. On the basis of these results, the mechanism of the crystallization of celluloses I and I is discussed. The effect of colony types, smooth and rough, on the formation of microfibrils in the presence of CMC is also described.     

A physico-chemical characterisation of new raw materials for microcrystalline cellulose manufacturing

A detailed physico-chemical characterisation of potential new cellulose sources (rice husk, hemp stalk, and coniferous needles), and microcrystalline cellulose (MCC) manufactured from them, was made in this work. The length and the width of the cellulose crystallites were determined by wide-angle X-ray scattering (WAXS), crystallinities were studied by means of WAXS and solid state cross polarisation magic angle spinning ¹³C nuclear magnetic resonance (NMR) spectroscopy, and the packing and the cross-sectional shape of the microfibrils were determined by small-angle X-ray scattering. When MCC was prepared from rice husks and hemp stalks an acceptable yield was obtained. Crystallinities obtained with solid state NMR spectroscopy and WAXS were highest for MCC prepared from hemp stalks, and lowest for rice husk MCC. The crystallite sizes of MCC samples studied in this work varied more than in those MCC samples which were prepared from conventional plant sources, and crystallite size and cellulose crystallinity were related. When taking into account rather high values of specific surface, hemp stalks and rice husks appear as a promising raw materials for MCC production.     

Thermal decomposition of native cellulose: Influence on crystallite size

The thermal degradation behavior of crystalline cellulose has been investigated using thermogravimetry, differential thermal analysis, and derivative thermogravimetry in a nitrogen atmosphere. Three cellulose samples, Halocynthia, cotton, and commercial microcrystalline cellulose Funacel, were used in this study to analyze the influence on crystallite size. They all belongs to cellulose I_β type and those crystallite sizes calculated from the X-ray diffractometry profiles by Scherrer equation were very different in the order Halocynthia > cotton > Funacel. The thermal decomposition of cellulose shifted to higher temperatures with increasing crystallite size. However, activation energies for the thermal degradation were the almost the same among the samples: 159-166 kJ mol⁻¹. These results indicated that the crystal structure does not affect the activation energy of the thermal degradation but the crystallite size affects the thermal degradation temperature.     

WAXS studies on block copolymers of ethylene and propylene

Wide-angle X-ray scattering from presumed block copolymers of polypropylene (PP) and ethylene-propylene copolymer (EPR), i.e., PP-EPR and PP-EPR-PP, synthesized by sequential polymerization with δ-TiCl₃? Et₂AlCl, was examined and compared with WAXS of mechanical blends and chain-transfer mixtures of PP and EPR with comparable compositions. The peak at 2θ = 20° for both the copolymers and the mixtures was attributed to the γ modification of PP in EPR. A strong variation in the ratio of diffraction intensities I₀₄₀/I₁₁₀ of PP in block copolymers and mixtures was explained in terms of crystallite growth in different directions. Analysis of the patterns and calculation of crystallinity, crystallite size, and lattice parameters led to the conclusion that block structure existed in the prepared copolymers.     

A native cellulose microfibril model

To aid in the understanding of cellulose ultrastructure, computer modelling has been employed to create a model of monoclinic (I) native cellulose. This was achieved by building a chain of cellulose, which was used in a two chain unit cell. An energy minimized microfibril model was created from several of these unit cells. A major advantage of this model is that it is a large scale unconstrained, isolated system. Thus, it facilitates the study of surface as well as central chains and provides a working model of a cellulose microfibril. An extensive analysis was carried out of intermolecular non-bond interactions and how they might contribute to the stability of the structure of crystalline native cellulose. 0969--0239 © 1998 Blackie Academic & Professional     

TEM study of the fibre cross-section attack in δ-Al2O3/Mg8Li metal matrix composites

During manufacturing of -Al₂O₃/Mg8Li composites by melt infiltration reactive diffusion of Mg and Li into the fibre bulk takes place. No remarkable reaction zone was found at the fibre periphery, although, a Mg enrichment zone (approx. 100 nm thick) was detected there by EDX and EELS. In addition, MgO, Li₂O and Mg₂Si minority phases were identified by SAED within the fibre cross-section.The crystalline structure of the -Al₂O₃ fibres in the Mg8Li matrix remained of the alumina spinel type at all the time, however, a set of crystallographically coherent products assigned as (Li) was detected by XRD and SAED within the fibre cross-section. As believed, the (Li) results from topotactic Li⁺ incorporation into the -Al₂O₃ lattice so that no significant changes in terms of size and morphology of the alumina crystallites are observed.     

In Situ crystallization of bacterial cellulose I. Influences of polymeric additives,stirring and temperature on the formation celluloses I α and I β as revealed by cross polarization/magic angle spinning (CP/MAS)13C NMR spectroscopy

To obtain further information about the formation of cellulose I and I, cross polarization/magic angle spinning (CP/MAS)¹³C NMR spectroscopy was used to study the effects of polymeric additives, stirring and culture temperature on the I When xyloglucan (XG) or carboxymethyl cellulose sodium salt (CMC) was added to the incubation medium, the amount of cellulose I decreased markedly, from a normal level of 64% to as low as 30%, with the most additive giving the lowest levels of I. Moreover, stirring causes mixtures containing even small amounts of XG to have a large effect. These results suggest that CMC or XG interferes with the aggregation of fibrillar units into the normal ribbon assemblies. It may be that there is a strain associated with this aggregation that results in the higher-energy I form. Thus, cellulose I may grow preferentially when the strain caused by aggregation is not present. Lower temperatures (36–10 °C) gave an increase in I (from 56 to 72%).     

Heterodinuclear PtRh and PtIr complexes with phosphinite groups as bridging ligands

Compounds of the general formula [Pt(²-L) {P(O)Ph2}- {P(OH)Ph₂}], where ²-L={²-S₂P(OEt)₂}^- (1) and {²-S₂CNEt₂}^- (2), react in THF solution with the dinuclear complex [{(cod)M(-OMe)}₂] (M = Rh^I or Ir^I) to give new heterodinuclear compounds of the type [(²-L)Pt{-P(O)Ph₂}₂M(cod)], where ²-L={²-S₂P- (OEt)₂}^-;; M=Rh^I (3), Ir^I (4) and ²-L = {²-S₂C-NEt₂}^-; M=Rh^I (5) and Ir^I (6). Compounds (3) and (4) react with an excess of CO, leading to displacement of the coordinated -diolefin (cod) and the formation of the dicarbonyl derivatives [{²-S₂P(OEt)₂}Pt{-P(O)-Ph₂}₂]M(CO)₂] [M=Rh^I (7), Ir^I (8)].All products were characterized by carbon and hydrogen microanalysis and by i.r. and n.m.r. spectroscopy {¹H and³¹ P(¹H)}.     

Electrochemical synthesis of metal nanoparticles using a polymeric mediator,whose reduced form is adsorbed (deposited) on an electrode

Efficient mediated electrosynthesis of nanocomposite Au@р(MVCA⁸⁺-co-St) (~6 nm), in which ultrasmall Au nanoparticles (Au-NP) were bound in nanocapsules of water-soluble nanoparticles of соpolymer р(MVCA⁸⁺-co-St) of tetraviologen calix[4]resorcinol (MVCA⁸⁺) with styrene (St), was accomplished by the reduction of Au^I in aqueous medium. The quanti- tative reduction of Au^I was carried out using the theoretically necessary amount of electricity and was not accompanied by the deposition of metal on the electrode. Radical cations of viologen units MV^?+ of the molecule р(MVCA^4?+-co-St) adsorbed on the electrode and π-dimers MV^?+···MV^?+ of π-polymers [р(MVCA^4?+-co-St)] _n deposited on the electrode act- ed as the reducing agents with respect to Au^I. During electrolysis, the nanoparticles agglo- merated to 37—50 nm. The nanocomposite particles dispersed in ethanol had sizes of 72±16 nm and also contained Au-NP with sizes of 51±8 and 19±3 nm. The catalytic activity of the nanocomposite in the reduction of p-nitrophenol with sodium borohydride was demon- strated. A similar reduction of AgCl nanoparticles (~250 nm) led to the formation of silver nanoparticles with crystallite sizes in the range of 7—11 nm, the process was inefficient, however, even when using 250% of electricity, an incomplete reduction of AgCl was still observed.