Decomposition behaviors of various crystalline celluloses as treated by semi-flow hot-compressed water

Various types of crystalline cellulose consisting of group I (cell I, III_I, IV_I) and group II (cell II, III_II, IV_II) prepared from cotton linter were adjusted for their degree of polymerization (DP) as starting materials. These celluloses were then treated by semi-flow hot-compressed water (HCW) at 230–270 °C/10 MPa/2–15 min to study their decomposition behaviors. The treatments performed resulted in residues of celluloses and water-soluble (WS) portions. Consequently, the crystallinity of the residues was found to remain the same, but the DP was reduced as the temperature increased. Additionally, X-ray diffractometry and Fourier transform-infrared analyses demonstrated that crystallographic changes occurred for residues of cell III_I, IV_I and III_II. Despite these changes, the overall results of the residues showed that group I has higher resistance to decomposing than group II. As for the WS portions, the yields of the hydrolyzed and degraded products were higher in group II than group I, indicating that group II is less resistant to decomposition by HCW treatment. Results for both the residues and WS portions are in agreement with each other, showing that the degree of difficulty of decomposition was higher in group I than group II. Therefore, the decomposition behaviors of the celluloses are due to differences in the crystalline forms.     

Cellulose polymorphism study with sum-frequency-generation (SFG) vibration spectroscopy: identification of exocyclic CH2OH conformation and chain orientation

Sum-frequency-generation (SFG) vibration spectroscopy is a technique only sensitive to functional groups arranged without centrosymmetry. For crystalline cellulose, SFG can detect the C6H₂ and intra-chain hydrogen-bonded OH groups in the crystal. The geometries of these groups are sensitive to the hydrogen bonding network that stabilizes each cellulose polymorph. Therefore, SFG can distinguish cellulose polymorphs (I_β, II, III_I and III_II) which have different conformations of the exocyclic hydroxymethylene group or directionalities of glucan chains. The C6H₂ asymmetric stretching peaks at 2,944 cm^?1 for cellulose I_β and 2,960 cm^?1 for cellulose II, III_I and III_II corresponds to the trans-gauche (tg) and gauche-trans (gt) conformation, respectively. The SFG intensity of the stretch peak of intra-chain hydrogen-bonded O–H group implies that the chain arrangement in cellulose crystal is parallel in I_β and III_I, and antiparallel in II and III_II.     

Partial crystalline transformation of solvated cellulose IIII crystals, reproduced by theoretical calculations

In hot-water molecular dynamics simulation at 370 K, four cellulose III_I crystal models, with different lattice planes and dimensions, exhibited partial crystalline transformations of (1 ?1 0) chain sheets, in which hydroxymethyl groups were irreversibly rotated from gt into tg conformations, accompanied by hydrogen-bond exchange from the original O3–O6 to cellulose-I-like O2–O6 bonds. The final hydrogen-bond exchange ratio was about 95 % for some of the crystal models after 50 ns simulation. The corrugated (1 ?1 0) chain sheet was converted to a cellulose-I-like flat chain sheet with a slightly right-handed twist. The 3D structures of the three types of isolated chain sheet models were optimized using density functional theory calculations to compare their stabilities without crystal packing forces. The cellulose Iβ (1 0 0) models were more stable than the cellulose III_I (1 ?1 0) models. The optimized structure of cellulose III_I (1 0 0) models deviated largely from the initial sheet form. It was proposed to the crystalline transformation from cellulose III_I to Iβ that conversion of the chain sheet structure first take place, followed by sliding of the chain sheet along the fiber axis.     

Structure conversions of cellulose IIII crystal models in solution state: a molecular dynamics study

This paper re-examines our previous molecular dynamics (MD) study on cellulose III_I crystal models with finite dimensions solvated in explicit water molecules. Eight crystal models, differing in a constituent lattice plane and dimensions, were studied. One calculation allowed for O–H and C–H bond stretching, and had a small time step of 0.5 fs. The other calculation adopted non-scaling factors of the 1–4 non-bonded interactions. As in our previous study, in the former MD calculations, six of the eight crystal models exhibited structure conversion with cooperative chain slippages generated by a progressive fiber bend. This converted the initial non-staggered chain packing of cellulose III_I into a near one-quarter staggering and gave the crystal model a triclinic-like configuration. In contrast, in the non-1–4 scaling MD calculations, all of the eight crystal models retained the initial cellulose III_I crystal structure. Another series of non-1–4 scaling MD calculations were performed for the four crystal models containing chains with a degree of polymerization (DP) of 40 at 370 K, which simulated hot water treatment to convert cellulose III_I to Iβ. Some of the hydroxymethyl groups irreversibly rotated from gt into tg conformation. This accompanied exchange of the intrasheet hydrogen bonding scheme along the (1 ?1 0) lattice plane from O2–O6 to O3–O6. The original corrugated (1 ?1 0) chain sheet was partly converted into a cellulose I-like flat chain sheet.     

Elastic modulus of the crystalline regions of cellulose polymorphs

The elastic modulus E_l of the crystalline regions of cellulose polymorphs in the direction parallel to the chain axis was measured by x-ray diffraction. The E_l values of cellulose I, II, III_I, III_II, and IV_I were 138, 88, 87, 58, 75 GPa, respectively. This indicates that the skeletons of these polymorphs are completely different from each other in the mechanical point of view. The crystal transition induces a skeletal contraction accompanied by a change in intramolecular hydrogen bonds, which is considered to result in a drastic change in the E_l value of the cellulose polymorphs. © 1995 John Wiley & Sons, Inc.     

The structure of the complex of cellulose I with ethylenediamine by X-ray crystallography and cross-polarization/magic angle spinning 13C nuclear magnetic resonance

X-ray crystallographic and cross-polarization/magic angle spinning ¹³C nuclear magnetic resonance techniques have been used to study an ethylenediamine (EDA)-cellulose I complex, a transient structure in the cellulose I to cellulose III_I conversion. The crystal structure (space group P2 ₁ ; a = 4.546 Å, b = 11.330 Å, c = 10.368 Å and γ = 94.017°) corresponds to a one-chain unit cell with one glucosyl residue in the asymmetric unit, a gt conformation for the hydroxymethyl group, and one EDA molecule per glucosyl residue. Unusually, there are no O–H···O hydrogen bonds between the cellulose chains; the chains are arranged in hydrophobic stacks, stabilized by hydrogen bonds to the amine groups of bridging EDA molecules. This new structure is an example of a complex in which the cellulose chains are isolated from each other, and provides a number of insights into the structural pathway followed during the conversion of cellulose I to cellulose III_I through EDA treatment.     

Synchrotron X-ray structures of cellulose I<Subscript>β</Subscript> and regenerated cellulose II at ambient temperature and 100 K

Synchrotron X-ray data have been collected to 1.4 Å resolution at the NE-CAT beam-line at the Advanced Photon Source from fibers of cellulose I_β and regenerated cellulose II (Fortisan) at ambient temperature and at 100 K in order to understand the effects of low temperature on cellulose more thoroughly. Crystal structures have been determined at each temperature. The unit cell of regenerated cellulose II contracted, with decreasing temperature, by 0.25%, 0.22% and 0.1% along the a, b, and c axes, respectively, whereas that of cellulose I_β contracted only in the direction of the a axis, by 0.9%. The value of 4.6×10^?5 K^?1 for the thermal expansion coefficient of cellulose I_β in the a axis direction can be explained by simple harmonic molecular oscillations and the lack of hydrogen-bonding in this direction. The molecular conformations of each allomorph are essential unchanged by cooling to 100 K. The room temperature crystal structure of regenerated cellulose II is essentially identical to the crystal structure of mercerized cellulose II.     

Hydrolysis behavior of various crystalline celluloses treated by cellulase of Tricoderma viride

Cellobiose and glucose are valuable products that can be obtained from enzymatic hydrolysis of cellulose. This study discusses changes in the crystalline form of celluloses to enhance the production of sugars and examines the effect on structural properties during enzymatic hydrolysis. Various crystalline celluloses consisting of group I (cell I, cell III_I, cell IV_I) and group II (cell II, cell III_II, cell IV_II) of similar DPs were prepared as starting materials. The similar DP values allowed a more direct comparison of the hydrolysis yields. The outcomes were analyzed and evaluated based on the residues and supernatants obtained from the treatment. As a result: (1) action of the cellulase of Trichoderma viride decreased both DP and crystallinity, with greater changes in group II celluloses, (2) the polymorphic interconversion process that occurred for cell III_I, cell IV_I, cell III_II and cell IV_II during the treatment was independent of the enzymatic hydrolysis, thus, the hydrolysis behaviors depended on the starting material of the celluloses, and (3) higher sugar production was obtained from cell III_I and group II. Therefore, the hydrolysis behavior of the various crystalline celluloses depended on the particular polymorph of the starting material.     

Mononuclear copper(II) complexes of bis-triazole-based macrocyclic Schiff base hydrazones: direct synthesis,EPR studies,magnetic and thermal properties

Mononuclear copper(II) complexes of 1,2,4-triazole-based Schiff base macrocyclic hydrazones, III and IV, have been reported. The prepared amorphous complexes have been characterized by spectroscopic methods, electron spray ionization mass spectrometry, and elemental analysis data. Electrochemical studies of the complexes in DMSO show only one quasi-reversible reduction wave at +0.43 V (ΔE = 70 mV) and +0.42 V (ΔE = 310 mV) for III and IV, respectively, which is assigned to the Cu(II) → Cu(I) reduction process. Temperature dependence of magnetic susceptibilities of III and IV has been measured within an interval of 2–290 K. The values of χ_M at 290 K are 1.72 × 10^?3 cm³ mol^?1 and 1.71 × 10^?3 for III and IV, respectively, which increases continuously upon cooling to 2 K. EPR spectra of III and IV in frozen DMSO and DMF were also reported. The trend g_|| > g⊥ > g_e suggests the presence of an unpaired electron in the d_x2?y2 orbital of the Cu(II) in both complexes. Furthermore, spectral and antimicrobial properties of the prepared complexes were also investigated.     

Quantifying the influence of dispersion interactions on the elastic properties of crystalline cellulose

Dispersion and electrostatic interactions both contribute significantly to the tight assembly of macromolecular chains within crystalline polysaccharides. Using dispersion-corrected density functional theory (DFT) calculation, we estimated the elastic tensor of the four crystalline cellulose allomorphs whose crystal structures that are hitherto available, namely, cellulose Iα, Iβ, II, III_I. Comparison between calculations with and without dispersion correction allows quantification of the exact contribution of dispersion to stiffness at molecular level.

     

Simulation of X-ray diffractograms relevant to the purported polymorphs cellulose IV<Subscript>I</Subscript> and IV<Subscript>II</Subscript>

Diffractograms were simulated for model nanocrystals of cellulose I_β, using numerical summation of radiation scattered from all carbon and oxygen atoms in the nanocrystal. Diffractogram peaks were sometimes displaced by a few degrees from positions calculated by the Bragg equation, as predicted in a published study based on a different mathematical approach. Simulated diffractograms showed 2 or 3 peaks, depending on the cross-sectional size and shape of the model nanocrystal. Some of the 2-peak diffractograms resembled published results for the purported polymorph cellulose IV_I, or for cell-wall cellulose, supporting suggestions that cellulose IV_I is simply cellulose I fragmented into nanocrystals with relatively small cross-sectional dimensions. A published diffractogram for cellulose IV_II could not be simulated with acceptable precision, suggesting that this polymorph might have a crystal structure distinctly different from that of cellulose I_β.     

Mechanism of structure formation of microbial cellulose during nascent stage

The structure of microbial cellulose (MC) produced by Acetobacter xylinum was studied in presence of Fluorescent Brightener, Direct Blue 1, 14, 15, 53, Direct Red 28, 75 and 79, as probe. X-ray diffraction pattern of the product showed that it was a crystalline complex of dye and cellulose. The product has the structure in which the monomolecular layer of the dye molecule is included between the cellulose sheets corresponding to the ( $ 1\bar{1}0 $ ) planes of microbial cellulose. As a result of dye inclusion, d-spacing of lower angle plane (100) of products becomes 8.0–8.8 Å instead of 6.1 Å of MC. The d-spacing for the higher angle plane must be (010) plane due to stronger van der Waals forces between the pyranose rings which reduced 5.3 Å space of (110) plane of MC to 3.9–4.5 Å in the product. However, cellulose regenerated from FB, DR28 products was cellulose I and IV, respectively, and that from each DB1, 14, 15, 53, DR75 and 79 products was cellulose II. Solid state ¹³C NMR and deuteration-IR showed the product was non-crystalline which was contrasted to X-ray results. The regenerated celluloses were cellulose I_β, IV_I and II, respectively. Thus the structure of the product depends on the characteristics of dye which affects the conformation of cellulose at the nascent stage by the direct interaction with cellulose chains. The different regenerated celluloses as well as different fine structure in the same cellulose allomorph were produced depending mainly on number and position of the sulfonate groups in the dye.     

Lateral thermal expansion of cellulose Iβ and IIII polymorphs

Measurements of the thermal expansion coefficients (TECs) of cellulose crystals in the lateral direction are reported. Oriented films of highly crystalline cellulose I_β and III_I were prepared and then investigated with X‐ray diffraction at specific temperatures from room temperature to 250 °C during the heating process. Cellulose I_β underwent a transition into the high‐temperature phase with the temperature increasing above 220–230 °C; cellulose III_I was transformed into cellulose I_β when the sample was heated above 200 °C. Therefore, the TECs of I_β and III_I below 200 °C were measured. For cellulose I_β, the TEC of the a axis increased linearly from room temperature at α_a = 4.3 × 10^?5 °C^?1 to 200 °C at α_a = 17.0 × 10^?5 °C^?1, but the TEC of the b axis was constant at α_b = 0.5 × 10^?5 °C^?1. Like cellulose I_β, cellulose III_I also showed an anisotropic thermal expansion in the lateral direction. The TECs of the a and b axes were α_a = 7.6 × 10^?5 °C^?1 and α_b = 0.8 × 10^?5 °C^?1. The anisotropic thermal expansion behaviors in the lateral direction for I_β and III_I were closely related to the intermolecular hydrogen‐bonding systems. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1095–1102, 2002     

Structure and photoluminescence of Zn(II) and Сd(II) complexes with chiral bis-pyridine containing fragments of natural (–)-α-pinene

Complexes ZnLCl₂ (I) and [CdLCl₂] _n (IV), where L is chiral bis-pyridine containing fragments of natural monoterpenoide (–)-α-pinene are synthesized. Single crystals of [ZnLCl₂]·CH₂Cl₂ (II), [ZnLCl₂]·i-PrOH (III), and IV compounds are grown. The crystal structures of II and III are composed of mononuclear ZnLCl₂ complex molecules and solvate CH₂Cl₂ and i-PrOH molecules; the coordination polyhedron of the zinc atom Cl₂N₂ is a distorted tetrahedron. According to the single crystal XRD data, complex IV is a 1D coordination polymer; the coordination core CdN₂Cl₄ is a distorted octahedron and Cl atoms are bridging ligands. In the structures of II, III, and IV the L molecule functions as a bidentate chelate ligand. In the solid phase, complexes I and IV exhibit photoluminescence in the visible range (λ_max 505 nm and 460 nm respectively). The band intensity in the photoluminescence spectra of I and IV complexes considerably exceeds the band intensity in the spectrum of free L.     

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.     

Crystal structures ofcatena-[diligatocadmium(II) tetra-μ-cyanocadmate(II)] host clathrates: Diamminecadmium(II) tetracyanocadmate(II)-benzene(1/2), diamminecadmium(II) tetracyanocadmate(II)-aniline(1/2), ethylenediaminecadmium(II) tetracyanocadmate(II)-aniline(1/2), and a novel type bis(aniline)cadmium(II) tetracyanocadmate(II)-aniline(2/1)

The crystal structures of the four title clathrate compounds Cd(NH₃)₂Cd(CN)₄ · 2C₆H₆,I, Cd(NH₃)₂Cd(CN)₄ · 2C₆H₅NH₂,II, Cd(NH₂CH₂CH₂NH₂)Cd(CN)₄ · 2 C₆H₅NH₂,III, and Cd(C₆H₅NH₂)₂Cd(CN)₄ · 0.5C₆H₅NH₂,IV, have been analyzed by single crystal X-ray diffraction methods. CompoundI crystallizes in the monoclinic space groupC2/c,a = 12.063(2),b = 12.174(2),c = 14.621(1) Å,β = 90.976(9)°,Z = 4,R = 0.042 for 2388 reflections;II: monoclinic C₂/c,a = 12.1951(9),b = 12.078(1),c = 14.6921(7) Å,β = 93.436(5)°,Z = 4,R = 0.039 for 2374 reflections;III: monoclinicCc,a = 11.027(1),b = 12.0767(9),c = 15.837(1) Å,β = 92.059(9)°,Z = 4,R = 0.041 for 2883 reflections; andIV: monoclinicP2₁/n,a = 15.169(2),b = 16.019(2),c = 8.866(1) Å,β = 95.73(1)°,Z = 4,R = 0.052 for 3612 reflections. The three-dimensionalcatena-[diamminecadmium(II) tetra-μ-cyanocadmate(II)] hosts ofI andII are substantially isostructural to that of the already known Hofmann-Td-type Cd(NH₃)₂Hg(CN)₄ · 2C₆H₆. The three-dimensional en-Td-typecatena-[catena-μ-ethylenediaminecadmium(II) tetra-μ-cyanocadmate(II)] host ofIII, reinforced by the catena-μ-en linking between the octahedral Cd atoms, accommodates the aniline as the guest with a monoclinic distortion from the tetragonal symmetry of the previously reported en-Td-type benzene clathrate. InIV dual behavior of aniline, one as the unidentate ligand in the three-dimensional host and the other as the guest in the cage-like cavity, has been demonstrated.     

Synthesis and properties of copper(II) complexes with a chiral dioxatetraazamacrocyclic ligand based on a natural monoterpene, (+)-3-carene

The copper(II) compounds [CuL](NO₃)₂ · H₂O (I), [CuL](ClO₄)₂ · H₂O (II), CuLCl₂ · 3H₂O (III), and CuLBr₂ · 4H₂O (IV), where L is a chiral dioxatetraazamacrocyclic ligand based on the natural monoterpene (+)-3-carene, have been synthesized. According to IR and EPR spectroscopy, L acts as a tetradentate chelating ligand coordinated through the N atoms of the NH and C=N groups. The NO ₃ ^? anions in I and the ClO ₄ ^? anions in II are outer-sphere. I and II have a planar coordination core CuN₄, III has a CuN₄ClO coordination core, and IV has a CuN₄Br₂ coordination core.     

New fluorochromatouranylates of alkali metals: Synthesis and structure

Four new fluorochromatouranylates, namely, K[UO₂(CrO₄)F] · 1.5H₂O (I), Rb[UO₂(CrO₄)F] · 1.5H₂O (II), Rb[UO₂(CrO₄)F] · 0.5H₂O (III), and Cs[UO₂(CrO₄)F] · 0.5H₂O (IV), have been synthesized, and their crystallographic characteristics have been determined. All the compounds crystallize in monoclinic system, space group P2₁/c, with the unit cell parameters a = 13.1744(5) Å, b = 9.4598(3) Å, c = 13.0710(4) Å, β = 103.746(1)°, Z = 4, R = 0.0235 (I); a = 13.5902(7) Å, b = 9.5022(4) Å, c = 13.2271(6) Å, β = 102.914(2)°, Z = 4, R = 0.0247 (II); a = 24.7724(8) Å, b = 12.6671(4) Å, c = 9.4464(3) Å, β = 97.661(1)°, Z = 8, R = 0.0448 (III); a = 25.725(1) Å, b = 12.8261(5) Å, c = 9.4929(4) β = 97.208(1)°, Z = 8 (IV). The pairs of compounds I and II and compounds III and IV are isostructural. Crystals of compounds I–III have been subjected to complete X-ray diffraction study. It has been established that the structures of compounds I–III are built of [UO₂(CrO₄)F] _n ^n? layers, which are parallel to the (100) plane and linked into a framework by alkali-metal cations located between layers, together with water molecules. The effect of topological and geometric isomerism on the structural features of 34 known uranyl compounds of the AT³M² crystallochemical group, to which the studied compounds I–III also belong, is discussed.     

Cellulose‐Builder: A toolkit for building crystalline structures of cellulose

Cellulose‐builder is a user‐friendly program that builds crystalline structures of cellulose of different sizes and geometries. The program generates Cartesian coordinates for all atoms of the specified structure in the Protein Data Bank format, suitable for using as starting configurations in molecular dynamics simulations and other calculations. Crystalline structures of cellulose polymorphs Iα, Iβ, II, and III_I of practically any size are readily constructed which includes parallelepipeds, plant cell wall cellulose elementary fibrils of any length, and monolayers. Periodic boundary conditions along the crystallographic directions are easily imposed. The program also generates atom connectivity file in PSF format, required by well‐known simulation packages such as NAMD, CHARMM, and others. Cellulose‐builder is based on the Bash programming language and should run on practically any Unix‐like platform, demands very modest hardware, and is freely available for download from ftp://ftp.iqm.unicamp.br/pub/cellulose‐builder. © 2012 Wiley Periodicals, Inc.