Cellulose fibers modified by Eu3+-doped yttria-stabilized zirconia nanoparticles

This paper describes a method for manufacturing luminescent cellulose fibers. Good optical properties of cellulose fibers under UV-C illumination were achieved by incorporating ZrO₂ (0.5?mol% of Eu³⁺) stabilized by Y₂O₃ (7?mol%) into the fiber structure’s particles. Fibers were obtained from 8?wt% cellulose solution in N-methylmorpholine N-oxide (NMMO) with the addition of a luminescent modifier in the range between 0.5 and 10?wt%. The physico-chemical and mechanical parameters and the structure of these fibers were examined.     

Thermal behavior of the highly luminescent poly(3-hydroxybutyrate):Eu(tta)3(H2O)2 red-emissive complex

The aim of this study has been to gain a fundamental understanding of the mechanisms governing thermal degradation of luminescent poly(3-hydroxybutyrate) (PHB). PHB was doped with diaquatris(thenoyltrifluoroacetonate) europium(III) complex, [Eu(tta)₃(H₂O)₂], and different luminescent systems were obtained. The thermal-stability of the luminescent films was discussed and the products of decomposition were analyzed. Thermal degradation of PHB:Eu(tta)₃ x % systems (x = 0, 1, 5, 10, and 15 %) was elucidated by means of thermogravimetric analysis (TG), the thermal-stability decreases with the increase of europium complex concentration. The PHB polymer decomposed with evolution of carbon dioxide and 2-butenoic acid molecules. The TG–FTIR results, of the gaseous degradation products of PHB in nitrogen atmosphere, indicated that the polymer is stable at temperatures up to 200 °C. Polymer matrix at concentrations above 5 % decomposed with evolution of water molecules among the other gaseous products, which implied the presence of a hydrated complex in the system. The luminescent films showed more flexibility due to a loss in crystallinity, which suggested a potential usefulness in technical applications.     

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.     

Synthesis of antibacterial cellulose materials using a “clickable” quaternary ammonium compound

Development of advanced functional materials from naturally abundant polymers such as cellulose are of significant importance. Of particular interest is embedding antibacterial functionality to cellulose materials to make permanent antibacterial materials and devices. In the present research, a “clickable” quaternary ammonium compound, N-(2-ethoxy-2-oxoethyl)-N,N-dimethylprop-2yn-1-aminium bromide (EdMPABr) was synthesized via a simple reaction with nearly stoichiometric yield and well characterized with 1D (¹H, ¹³C) and 2D (COSY, HSQC) NMR and ATR-FTIR. EdMPABr can be covalently bonded to many molecules containing an azido group to form non-leaching antibacterial materials via the simple Cu(I)-catalyzed alkyne-azide [2 + 3] cycloaddition reaction. As an example, EdMPABr was attached to our previously reported 3-O-azidopropoxypoly(ethylene glycol)-2,6-di-O-thexyldimethylsilyl cellulose (3-N₃PEG-2,6-TDMS cellulose, DS = 0.54 at C3 determined by ¹H NMR). Significant antibacterial activity of the synthesized 3-O-quaternary ammonium-2,6-di-O-thexyldimethylsilyl cellulose (3-QA-2,6-TDMS cellulose, DS = 0.30 at C3 determined by using N content from elemental analysis) was confirmed by testing against the representative bacteria Escherichia coli. By linking the EdMPABr to the honeycomb film of 3-N₃PEG-2,6-TDMS cellulose, the formed honeycomb film exhibited both antibacterial and antifouling properties. This research provides a simple and robust route towards the development of permanent antibacterial materials and biomedical devices.     

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.     

Pyrolysis kinetics of elephant grass pretreated biomasses

The Elephant Grass (Pennisetum purpureum Schum) was pretreated by two independent processes, through washing with hot water (W-EG) and acid solution (AW-EG) to improve its energy properties to apply it in a thermochemical process conversion into fuel. The biomasses were analyzed by proximate and ultimate analysis; and the pyrolysis kinetics, before and after pretreatments, were evaluated by the apparent activation energy (E _a) for decomposition in the temperature range of greater volatile matter through the Model-free kinetics using thermogravimetric analysis data. The kinetics of the microcrystalline cellulose Avicel PH-101 was performed to evaluate the E _a result of pure cellulose. The pretreatments were efficient in increasing the volatile matter and heating value, decreasing moisture and ash content, and improving its energetic power to the application in fast pyrolysis process for bio-oil production. The TG results have shown that the reduction in ash content facilitates the pyrolysis process, increasing the volatile matter and decreasing the apparent activation energy required to biomasses degradation, due to less diffusional resistances to heat and mass transfer of W-EG and AW-EG. The Avicel PH-101 showed the highest value of apparent activated energy (E _a = 276.2 kJ mol^?1) which could be explained by its crystallinity, suggesting that crystalline cellulose regions are less accessible to heat diffusion than amorphous regions, requiring more energy to its degradation.     

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.     

Hydrothermal homogeneous urea precipitation of hexagonal YBO3:Eu nanocrystals with improved luminescent properties

Well-crystallized YBO₃:Eu³⁺ nanocrystals were prepared by a mild hydrothermal method in the presence of urea, and a pure hexagonal phase could be obtained at a low temperature of 200°C only. The photoluminescence spectra showed a remarkable improvement on the chromaticity as well as the luminescent intensity, compared with the samples synthesized by solid-state reaction (SR). The effects of the synthesis temperature, urea concentration, and the doping concentration of Eu³⁺ on the crystallization and luminescent properties were investigated. The results showed that both high temperature and low urea concentration were favorable to the formation of YBO₃:Eu³⁺, and the ratio of red emission (⁵D₀→⁷F₂) to orange emission (⁵D₀→⁷F₁) increased with decreasing the synthesis temperature and the urea concentration. Furthermore, the samples exhibited a higher quenching concentration of Eu³⁺ in comparison with those prepared by the SR, which was beneficial to further enhancing the luminescent intensity. These synthesis-dependent phenomena were analyzed, and possible explanations were proposed.     

Affinity Adsorption Solid Substrate‐Room Temperature Phosphorimetry for the Determination of Alkaline Phosphatase

Abstract

In the presence of Pb(Ac)₂, the silicon dioxide nanoparticle containing rhodamine 6G (R‐SiO₂) can emit strong and stable solid substrate‐room temperature phosphorescence (SS‐RTP) signal on the surface of acetyl cellulose membrane (ACM) at λ_ex/λ_em=482/649 nm. It was found in the research that specific affinity adsorption reaction between triticum vulgare lectin (WGA) (which was labeled with luminescent silicon dioxide nanoparticle) and alkaline phosphatase (AP) can be carried out on the surface of ACM. The product of the reaction can emit stronger SS‐RTP signal. A new method of SS‐RTP for the determination of AP was established, based on an affinity adsorption reaction between AP and WGA labeled with nanoparticles containing rhodanime 6G luminescent molecules. The linear range of this WGA‐AP‐WGA‐R‐SiO₂ method is 1.00–360.00 ag AP spot^?1 (sample volume: 0.40 µL spot^?1, corresponding concentration range: 2.50–900.00 fg mL^?1). The regression equation of working curve is ΔIp=16.24+0.8856 m_AP (ag spot^?1), r=0.9993. Detection limit of this method calculated by 3S_b/k is 0.14 ag spot^?1. After 11‐fold replicate measurements, RSD are 3.9% and 3.1% for the systems containing 1.00 and 360.00 ag AP spot^?1, respectively. Compared with R‐SiO₂‐WGA‐AP method (detection limit: 0.45 ag spot^?1, corresponding concentration range: 2.00–320.00 ag spot^?1), the sensitivity of WGA‐AP‐WGA‐R‐SiO₂ method was obviously improved and the linear range was wider. The sensitivity, accuracy, and precision of this method are high. It has been successfully applied to determine AP in human serum.     

Iα → Iβ transition of cellulose under ultrasonic radiation

Aqueous suspensions of dispersed Glaucocystis cellulose microfibrils were sonicated at 4 °C for 3 h, using 24 kHz ultrasonic waves. This treatment induced a variety of ultrastructural defects, as the microfibrils became not only shortened, but also presented substantial damage materialized by kinks and subfibrillation. Upon analysis by X-ray diffraction and ¹³C solid-state NMR spectroscopy, it was found that the initial sample that contained 90 % of cellulose I_α allomorph became, to a large extent, unexpectedly converted into the I_β phase, while the loss of crystallinity was only moderate during the sonication treatment.     

Homogeneous alkalization of cellulose in <Emphasis Type="Italic">N</Emphasis>-methylmorpholine-<Emphasis Type="Italic">N</Emphasis>-oxide/water solution

Alkali cellulose is an important intermediate in the production of cellulose derivatives. N-methylmorpholine-N-oxide (NMMO)/H₂O was used as a homogeneous reaction medium for the cellulose alkalization process to intensify the alkalization degree and improve the substitution uniformity. The morphology, specific surface area and crystalline structure of pristine cellulose, the as-synthesized alkali cellulose and dissolved-regenerated cellulose were characterized by SEM, BET, XRD and FT-IR, respectively. The results showed that the homogeneous reaction medium not only offered a low mass transfer resistance, but also facilitated a disruption of the hydrogen bond in cellulose, thus resulting in the transformation of the cellulose structure from complicated stacking chains to simple glucose chains. The interior hydroxyl groups in the cellulose became accessible to the alkaline reagent NaOH to enhance the alkalization process for the increase in bonding alkali content and the improvement in substitution uniformity. The bonding alkali content was calculated by the difference between total added alkali and free alkali and was achieved as 0.61 g/g cellulose at the optimized operation conditions: reaction temperature of 95 °C, reaction time of 90 min, NMMO dosage of 90.00 g, cellulose 1.0 g and NaOH concentration of 1.40 wt%. Meanwhile, in the conventional alkalization process, the bonding alkali content was just 0.41 g/g cellulose. The alkali cellulose prepared in NMMO/H₂O medium has a large specific surface area of 125 m² g^?1 and an extremely low crystallinity degree. The NMMO/H₂O system represents a potential homogeneous solvent for the cellulose alkalization process.     

Luminescent cellulose fibers activated by Eu3+-doped nanoparticles

UV- active cellulose fibers were obtained by dry-wet method spinning an 8?% by weight α-cellulose solution in N-methylomorpholine-N-oxide (NMMO) modified by europium-doped gadolinium oxyfluoride Gd₄O₃F₆:Eu³⁺ containing 5?mol (%) of the dopant. Photoluminescent nanoparticles were introduced in the in powder form into a polymer matrix during the process of cellulose dissolution in NMMO. The dependencies of emission intensity on excitation energy and the concentration of Gd₄O₃F₆:Eu³⁺ nanoparticles in the final cellulosic products were examined by photoluminescence spectroscopy (excitation and emission). The fiber structure was studied by X-ray powder diffraction analysis. The size and dispersity of the nanoparticles in the polymer matrix were evaluated using scanning electron microscopy and X-ray microanalysis. The influence of different concentration particles (in the range from 0.5 to 5?% by weight) on the mechanical properties of the fibers, such as tenacity and elongation at break, were determined.     

Frequency dependent ferroelectric and electrical properties of (Ho, Ni) co-doped BiFeO3 thin films

We have evaluated the ferroelectric and electrical properties of pure BiFeO₃ (BFO) and (Bi_0.9Ho_0.1)(Fe_1?xNi_x)O_3?δ (BHFN_xO, x = 0.01, 0.02, and 0.03) thin films as frequency varying from 1 to 50 kHz on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. With the frequency from 1 to 10 kHz, the decrease of remnant polarization (2P _r ) of the BHFN_0.02O thin film was about 27 %, from 26 to 19 μC/cm², which is one half lower than those of the BHFN_xO (x = 0.01 and 0.03) thin films. Otherwise, the variation of the coercive electric field (2E _c ) was relatively small, which were 16, 11 and 3 % for the BHFN_xO (x = 0.01, 0.02, and 0.03) thin films. The remnant polarization (2P _r ) and the coercive electric field (2E _c ) values of the BHFN_0.02O thin film show the dependence of measurement frequency and it has been fairly saturated about 30 kHz. Also, the leakage current density of the co-doped BHFN_0.02O thin film showed three orders lower than that of the pure BFO, 2.14 × 10^?6 Å/cm² at 100 kV/cm.     

Rapid dissolution of spruce cellulose in H<Subscript>2</Subscript>SO<Subscript>4</Subscript> aqueous solution at low temperature

Dissolution of cellulose is the key challenge in its applications. It has been discovered that spruce cellulose with high molecular weight (4.10 × 10⁵ g mol^?1) can be dissolved in 64 wt% H₂SO₄ aqueous solution at low temperature within 2 min, and the cellulose concentration in solution can reach as high as 5 % (w/v). FT-IR spectra and XRD spectra proved that it is a direct solvent for cellulose rather than a derivative aqueous solution system. The cold H₂SO₄ aqueous solution broke the hydrogen bonds among cellulose molecules and the low temperature dramatically slowed down the hydrolysis, which led to the dissolution of cellulose. The resultant cellulose solution was relatively stable, and the molecular weight of cellulose only slightly decreased after storage at ?20 °C for 1 h. Due to the high molecular weight of cellulose, cellulose solution could form regenerated films with good mechanical properties and transparency at low concentration (2 % w/v). This work has not only provided the new evidence of cellulose dissolution which facilitated the development of cellulose solvent, but also suggested a convenient way to directly transfer cellulose with high molecular weight into materials without structure modifications.     

Fluorescent cellulose aerogels containing covalently immobilized (ZnS)x(CuInS2)1−x/ZnS (core/shell) quantum dots

Photoluminiscent (PL) cellulose aerogels of variable shape containing homogeneously dispersed and surface-immobilized alloyed (ZnS)_x(CuInS₂)_1?x/ZnS (core/shell) quantum dots (QD) have been obtained by (1) dissolution of hardwood prehydrolysis kraft pulp in the ionic liquid 1-hexyl-3-methyl-1H-imidazolium chloride, (2) addition of a homogenous dispersion of quantum dots in the same solvent, (3) molding, (4) coagulation of cellulose using ethanol as antisolvent, and (5) scCO₂ drying of the resulting composite aerogels. Both compatibilization with the cellulose solvent and covalent attachment of the quantum dots onto the cellulose surface was achieved through replacement of 1-mercaptododecyl ligands typically used in synthesis of (ZnS)_x(CuInS₂)_1?x/ZnS (core–shell) QDs by 1-mercapto-3-(trimethoxysilyl)-propyl ligands. The obtained cellulose—quantum dot hybrid aerogels have apparent densities of 37.9–57.2 mg cm^?3. Their BET surface areas range from 296 to 686 m² g^?1 comparable with non-luminiscent cellulose aerogels obtained via the NMMO, TBAF/DMSO or Ca(SCN)₂ route. Depending mainly on the ratio of QD core constituents and to a minor extent on the cellulose/QD ratio, the emission wavelength of the novel aerogels can be controlled within a wide range of the visible light spectrum. Whereas higher QD contents lead to bathochromic PL shifts, hypsochromism is observed when increasing the amount of cellulose at constant QD content. Reinforcement of the cellulose aerogels and hence significantly reduced shrinkage during scCO₂ drying is a beneficial side effect when using α-mercapto-ω-(trialkoxysilyl) alkyl ligands for QD capping and covalent QD immobilization onto the cellulose surface.     

Effect of Sr2+ doping on the luminescence properties of YVO4:Eu3+,Sr2+ particles prepared by a solvothermal method

Well-dispersed Eu³⁺ and Sr²⁺ co-doped YVO₄ luminescent particles (YVO₄:Eu³⁺,Sr²⁺) on the submicron scale were prepared by a facile solvothermal method at low temperature. The effect of Sr²⁺ doping on the luminescence of YVO₄:Eu³⁺,Sr²⁺ particles was investigated by fixing the Eu³⁺ doping concentration at 7 mol%. It was found that the luminescence intensity of the as-prepared YVO₄:Eu³⁺,Sr²⁺ particles increased with the Sr²⁺ doping concentration x to reach a two-fold enhancement when x = 5 %, and then decreased for higher x. We also investigated the effect of thermal annealing on the luminescence properties of the YVO₄:Eu³⁺ and YVO₄:Eu³⁺,Sr²⁺ particles. A remarkable enhancement in their luminescence properties was observed after annealing at 900 °C in air for 30 min. It was showed that the annealed YVO₄:Eu³⁺,Sr²⁺ particles exhibited a two-fold stronger emission than the annealed YVO₄:Eu³⁺. This work indicates that Sr²⁺ doping is beneficial to the luminescence enhancement for both the as-prepared and annealed YVO₄:Eu³⁺,Sr²⁺ particles.     

NMR spectroscopic studies on dissolution of softwood pulp with enhanced reactivity

N-methylmorpholine N-oxide (NMMO) is a known cellulose solvent used in industrial scale (LyoCel process). We have studied interactions between pretreated softwood pulp fibers and aqueous NMMO using nuclear magnetic resonance (NMR) spectroscopic methods, including solid state cross polarisation magic angle spinning (CP-MAS) ¹³C and ¹⁵N spectroscopies, and ¹H high resolution MAS NMR spectroscopy. Changes in both cellulose morphology and in accessibility of solvents were observed after the pulp samples that were exposed to solvent species were treated at elevated temperature. Evidence about interactions between cellulose and solvent components was observed already after a heat treatment of 15 min. The crystalline structure of cellulose was seen to remain intact for the first 30 min of heat treatment, at the same time there was a re-distribution of solvent species taking place. After a 90 min heat treatment the crystalline structure of cellulose had experienced major changes, and potential signs of regeneration into cellulose II were observed.     

Controlled incorporation of deuterium into bacterial cellulose

Isotopic enrichment has been widely used for investigating the structural and dynamic properties of biomacromolecules to provide information that cannot be carried out with molecules composed of natural abundance isotopes. A media formulation for controlled incorporation of deuterium in bacterial cellulose synthesized by Gluconacetobacter xylinus subsp. sucrofermentans is reported. The purified cellulose was characterized using Fourier Transform Infra-Red spectrophotometry and mass spectrometry which revealed that the level of deuterium incorporation in the perdeuterated cellulose was greater than 90 %. Small-angle neutron scattering analysis demonstrated that the overall structure of the cellulose was unaffected by the substitution of deuterium for hydrogen. In addition, by varying the amount of D-glycerol in the media it was possible to vary the scattering length density of the deuterated cellulose. A large disk model was used to fit the curves of bacterial cellulose grown using 0 and 100 % D-Glycerol yielding a lower bound to the disk radii, R _min = 1,132 ± 6 and 1,154 ± 3 Å and disk thickness, T = 128 ± 1 and 83 ± 1 Å for the protiated and deuterated forms of the bacterial cellulose, respectively. This agrees well with the scanning electron microscopy analysis which revealed stacked sheets in the cellulose pellicles. Controlled incorporation of deuterium into cellulose will enable new types of experiments using techniques such as neutron scattering to reveal information about the structure and dynamics of cellulose and its interactions with proteins and other (bio) polymers.     

The electrochemical properties of Fe- and Ni-cosubstituted Li2MnO3 via combustion method

The Co-free Li_1.20Mn_0.54Ni _x Fe _y O₂ (x/y?=?0.5, 1.0, 2.0) materials were synthesized by combustion method. The effects of the preparation condition on the structure, morphology, and electrochemical performance were investigated by X-ray diffractometry, scanning electron microscopy, charge–discharge tests, and cyclic voltammetry (CV). The results indicate that the structure and electrochemical characteristics are sensitive to the preparation condition when a large amount of Fe is included. A pure layered α-NaFeO₂ structure with R-3m space group and the discharge capacities of over 200 mAh g^?1 were observed in some as-prepared cathode materials. Particularly, the Li_1.2Mn_0.54Ni_0.13Fe_0.13O₂ prepared by mixing an excess amount of lithium and by firing at 600 °C exhibits a second discharge capacity of 264 mAh g^?1 in the voltage range of 1.5–4.8 V under current density of 30 mA g^?1 at 30 °C and discharge capacity of 223 mAh g^?1 at 2.0–4.8 V. Nevertheless, an unpleasant capacity fading was observed and is primarily ascribed to transformation from a rock-layered structure into a spinel one according to CV testing.     

Syntheses and Crystal Structures of Two New Pentaborates Templated by Transition-Metal Complexes

Two new pentaborates [M(dap)₃][B₅O₆(OH)₄]₂·H₂O (M = Co (1) and Ni (2); dap = 1,2-diaminopropane) have been hydrothermally synthesized. Both structures were determined by single crystal X-ray diffraction and further characterized by elemental analysis, FT-IR, thermogravimetric analysis and photoluminescence spectroscopy. Two compounds are isostructural and consist of isolated pentaborate [B₅O₆(OH)₄]^? anions and [M(dap)₃]²⁺ complex cations. The anionic [B₅O₆(OH)₄]^? groups are linked by extensive hydrogen bonds to form a 3-D supramolecular framework with large channels, in which the transition-metal complex templates are located. The luminescent properties of 1 and 2 were studied, and blue luminescence occurs with an emission maximum at 405 and 408 nm upon excitation at 332 and 328 nm respectively. Crystal data: 1, monoclinic, space group P2₁/c (No. 14), a = 9.7159(5) Å, b = 29.3372(19) Å, c = 11.5121(6) Å, β = 103.286(5)°, V = 3193.6(3) ų, Z = 4; 2, monoclinic, space group P2₁/c, a = 9.7264(4) Å, b = 29.3810(16) Å, c = 11.5185(6) Å, β = 103.249(4)°, V = 3204.0(3) ų, Z = 4.