Changes of cellulose fiber wall structure during drying investigated using NMR self-diffusion and relaxation experiments

The self-diffusion of water sorbed in cellulose fibers was investigatedby means of NMR during slow drying in order to follow changes in the celluloseporous structure. In pulp fibers pores with at least one dimension on them scale were observed at high amounts of sorbed water and nm-scale pores atlow amounts. Beating affected the m-scale pores. Regenerated cellulosefibers had nm-scale pores up to high amounts of water. Bulk water was observedas a second component with long T ₂ in a CPMGexperiment. The sequence of water removal for kraft pulp fibers is: (1) bulkwater, (2) water in m-scale pores and (3) water in nm-scale pores.     

TPAOH/NaOH混合碱体系对ZSM-5沸石的改性及其催化性能研究

采用四丙基氢氧化铵和氢氧化钠有机无机混合碱TPAOH/NaOH体系对ZSM-5分子筛进行改性处理,得到了具有介孔和微孔的ZSM-5分子筛。用XRD、N₂吸附脱附、NH₃-TPD、SEM等手段对改性后的产物进行表征。结果表明,碱处理ZSM-5分子筛会使分子筛同时脱硅和脱铝。当混合碱体系中总OH^-浓度一定时,随TPA⁺/OH^-比值的降低和处理时间的延长,均会使分子筛的微孔结构数量减少,介孔结构数量增加。同时,还会改变分子筛的酸性,TPA⁺/OH^-比值适合的混合碱体系可在生成介孔的同时最大限度保留微孔结构,并减少分子筛的强酸数量,在甲醇制烯烃反应(MTO)中表现出较高的丙烯选择性。与无机碱NaOH相比,TPAOH对分子筛的改性速率较慢而且温和,具有可控性,可以起到孔道生长调节剂的作用。     

Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions

Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions was studied systematically. The dissolution behavior and solubility of cellulose were evaluated by using (13)C NMR, optical microscopy, wide-angle X-ray diffraction (WAXD), FT-IR spectroscopy, DSC, and viscometry. The experiment results revealed that cellulose having viscosity-average molecular weight ((overline) M eta) of 11.4 x 104 and 37.2 x 104 could be dissolved, respectively, in 7% NaOH/12% urea and 4.2% LiOH/12% urea aqueous solutions pre-cooled to -10 degrees C within 2 min, whereas all of them could not be dissolved in KOH/urea aqueous solution. The dissolution power of the solvent systems was in the order of LiOH/urea > NaOH/urea > KOH/urea aqueous solution. The results from DSC and (13)C NMR indicated that LiOH/urea and NaOH/urea aqueous solutions as non-derivatizing solvents broke the intra- and inter-molecular hydrogen bonding of cellulose and prevented the approach toward each other of the cellulose molecules, leading to the good dispersion of cellulose to form an actual solution.     

Toughness enhancement of cellulose nanocomposites by alkali treatment of the reinforcing cellulose nanofibers

Nanocomposites were produced with NaOH aqueous solution-treated microfibrillated cellulose (MFC) and phenolic resin, and the mechanical properties were compared with their microcomposite counterparts based on pulp fiber. Tensile tests showed that strong alkali-treated MFC nanocomposites with resin content around 20 wt.% achieved strain at fracture values two times higher than those of untreated MFC nanocomposites and five times higher than those of untreated pulp microcomposites. The improvement in work of fracture of alkali-treated MFC nanocomposites was attributed to the ductility of the nanofibers caused by transformations in the amorphous regions along the cellulose microfibrils.     

Dielectric spectroscopy of nanocomposites based on iPP and aPS treated in the water solutions of alkali metal salts

In this paper, a new simple and environmentally friendly treatment technique for obtaining polymer nanocomposites with appropriate dielectric properties has been presented. Sheets of isotactic polypropylene and atactic polystyrene were immersed in 3 saturated water solutions of alkali metal salts (LiCl, NaCl, and KCl) at 2 fixed temperatures (23°C and 90°C), and 3 DC electrical potentials (+4 kV, −4 kV, and ground potential) were applied. A quantification of alkali metals in the polymer sheets was conducted by inductively coupled plasma optic emission spectrometry. The obtained concentration values were from 7.38·10⁻⁹ mol/cm³ to 1.25·10⁻⁷ mol/cm³. The qualitative analysis of potassium distribution in the polymer matrix was conducted by time‐of‐flight secondary ion mass spectrometry cross‐sectional record. The relative dielectric constant (ε′) of samples was investigated in the frequency range from 20 Hz to 9 MHz at the constant temperature of 22°C. Stable values of ε′ in fully measured frequency range were observed for both pure and treated samples. Next, the results of the dielectric spectroscopy measurements were compared and established the kind of treatment that provided the highest value of ε′. The relationship between the concentrations of alkali metals and the values of relative dielectric constant was determined for the samples obtained by a treatment at 90°C and +4 kV.     

Changes in cellulose supramolecular structure and molecular weight distribution during steam explosion of aspen wood

We have studied the cellulose supramolecular structure in pulps obtainedby steam explosion of aspen wood. The pulps were bleached with hydrogenperoxidein an OQP-sequence and characterised by size exclusion chromatography and¹³C cross polarisation magic angle spinning (CP/MAS)NMR-spectroscopy. With CP/MAS-NMR-spectroscopy and chemometrics we were able toseparate the supramolecular structural changes taking place during steamexplosion into two independent processes. One process was related to the extentof processing and showed degradation and dissolution of cellulose,hemicelluloseand lignin accompanied by an increase in cellulose content. The second processwas displayed by pulps having molecular weights below approximately 100000 andwas interpreted as showing the removal of dislocations and an increase incrystalline and/or paracrystalline cellulose in the cellulose fibrils.     

混合碱处理制备微介孔催化剂及其噻吩烷基化催化性能

以SiO_2/Al2O3物质的量比为50的H-ZSM-5分子筛为母体,分别采用Na_2CO_3溶液处理后加入TPAOH溶液进行二次晶化法以及Na_2CO_3/TPAOH混合溶液同时处理法,制备了微孔-介孔多级孔HZSM-5催化剂,对其噻吩烷基化反应催化性能进行了研究。结果表明,采用4 mol/L的Na_2CO_3溶液处理后的催化剂在TPAOH溶液中发生了二次晶化;当TPAOH溶液浓度为0.3 mol/L、晶化温度为170℃、晶化时间为24 h时,得到的HZ(CO_2-3-TPA+,0.3-24-170)催化剂具有适宜的孔径和酸性,其噻吩烷基化转化率最高(99.1%)。而Na_2CO_3/TPAOH同时处理HZSM-5分子筛所得的催化剂,由于生成大量SiO_2堵塞了孔道,覆盖了催化剂表面,降低了催化剂的平均孔径和酸性,不适合噻吩烷基化反应。     

Reduced Arene Complexes of Scandium

Alkali metal naphthalenide or anthracenide reacted with scandium(III) anilides [Sc(X){N(tBu)Xy}₂(thf)] (X=N(tBu)Xy ( 1 ); X=Cl ( 2 ); Xy=C₆H₃-3,5-Me₂) to give scandium complexes [M(thf)_n][Sc{N(tBu)Xy}₂(RA)] (M=Li–K; n=1–6; RA=C₁₀H₈²⁻ ( 3-Naph-K ) and C₁₄H₁₀²⁻ ( 3-Anth-M )) containing a reduced arene ligand. Single-crystal X-ray diffraction revealed the scandium(III) center bonded to the naphthalene dianion in a σ²:π-coordination mode, whereas the anthracene dianion is symmetrically attached to the scandium(III) center in a σ²-fashion. All compounds have been characterized by multinuclear, including ⁴⁵Sc NMR spectroscopy. Quantum chemical calculations of these intensely colored arene complexes confirm scandium to be in the oxidation state +3. The intense absorptions observed in the UV/Vis spectra are due to ligand-to-metal charge transfers. Whereas nitriles underwent C−C coupling reaction with the reduced arene ligand, the reaction with one equivalent of [NEt₃H][BPh₄] led to the mono-protonation of the reduced arene ligand.     

Lithium-7, sodium-23, and cesium-133 NMR and far infrared study of alkali complexes with C222-dilactam in various solvents

Nuclear magnetic resonances of alkali nuclei,⁷Li,²³Na, and¹³³Cs, as well as far infrared measurements are used to study alkali complexes of a bicyclic diazapolyoxa ligand—the dilactam of cryptand C222. Measurements were carried out in pyridine, tetrahydrofuran, acetonitrile, nitromethane, dimethylformamide, and aqueous solutions. The complexing ability of the dilactam is similar to, but weaker than, that of the cryptand C222. The limiting chemical shifts of the complexed cations were solvent-dependent, indicating incomplete enclosure of the cation by the ligand. Formation constants of Li⁺ and Cs⁺ complexes were calculated from the chemical-shift dependence on the ligand/metal ion mole ratio.     

Spectroscopic properties in the liquid phase: combining high-level ab initio calculations and classical molecular dynamics.

We present an integrated computational tool, rooted in density functional theory, the polarizable continuum model, and classical molecular dynamics employing spherical boundary conditions, to study the spectroscopic observables of molecules in solution. As a test case, a modified OPLS-AA force field has been developed and used to compute the UV and NMR spectra of acetone in aqueous solution. The results show that provided the classical force fields are carefully reparameterized and validated, the proposed approach is robust and effective, and can also be used by nonspecialists to provide a general and powerful complement to experimental techniques.     

langmuir aggregation of alkali blue 6b in proteins: Study and application

The formation of microelectrostatic fields in biopolymers causes the adsorption of stain molecules in protein. The interactions between the dye alkali blue 6B (AB6B) and four proteins, bovine serum albumin (BSA), human γ-globulin (γ-G), horse myoglobin (Mb) and ovalbumin (OVA), were studied by the microphase adsorption/spectral correction technique. It was observed that the interactions obey the Langmuir isothermal adsorption. The Langmuir equilibrium constants of all the aggregates were determined. Interestingly, the adsorption of AB6B has no relation to the array sequence of amino acid residues, and an electrostatic field consists of constant amino acid residues. The novel method has been applied satisfactorily to the determination of the total protein content in two different samples.

     

Mechanical and thermal properties of Acacia leucophloea fiber/epoxy composites: Influence of fiber loading and alkali treatment

In this work, the influence of fiber content and alkali treatment on the mechanical and thermal properties of Acacia leucophloea fiber-reinforced epoxy composites was studied. Ten composite samples were fabricated by varying fiber content (5, 10, 15, 20, and 25 wt%); both untreated and treated fiber were soaked in a 5% NaOH solution for 45 min by using hand-layup method. The composite reinforced with 20 wt% treated fiber content exhibited better mechanical properties and thermal properties. Fourier transform infrared analysis, morphological analysis by atomic force microscope, and scanning electron microscope of composites were also performed.     

Cold NaOH/urea aqueous dissolved cellulose for benzylation: Synthesis and characterization

Cold NaOH/urea aqueous dissolved cellulose was studied for the synthesis of benzyl cellulose by etherification with benzyl chloride. By varying the molar ratios of benzyl chloride to OH groups in cellulose (1.5–4.0) and reaction temperatures (65–70 °C), benzyl cellulose with a degree of substitutions (DS) in the range of 0.29–0.54 was successfully prepared under such mild conditions. The incorporation of benzyl groups into cellulose was evidenced by multiple spectroscopies, including FT IR, ¹H NMR, ¹³C NMR, CP/MAS ¹³C NMR and XRD. In addition, the thermal stability and surface morphology of the benzyl cellulose was also investigated with regard to the degree of substitution. The results indicated that the benzyl cellulose product with a low DS (0.51) in the present study reached the same solubility in many organic solvents as compared to those prepared in heterogeneous media. After benzylation, the sample decomposed at a lower temperature with a wider temperature range, which indicated that the thermal stability of benzyl cellulose was lower than that of the native cellulose. In addition, benzylation resulted in a pronounced reduction in crystallinity as well as a fundamental alteration of morphology of the native cellulose.     

Stability and Conversion of Tin Zintl Anions in Liquid Ammonia Investigated by NMR Spectroscopy

Homoatomic polyanions of post‐transition main‐group metals, namely, Zintl anions, are precast in analogous Zintl phases and can react in solution to form new materials. Despite comprehensible reaction approaches, the formed products cannot be planned in advance, as hitherto undetected and therefore disregarded side reactions take place. The outcomes and interpretations of the reactions of Zintl anions are so far based mainly on crystal structures, which only allow characterization of the product that has the lowest solubility. Here we present the results of our investigation of the stability of highly charged tin Zintl anions in liquid ammonia, which is not exclusively based on solution effects but also on the oxidative influence of the solvent. This allows for a deeper understanding of the ongoing processes in solution and opens doors to the directed synthesis of transition metal complexes of Sn₄^4?, here shown by its reactivity towards MesCu.     

Homogeneous methylation of wood pulp cellulose dissolved in LiOH/urea/H2O

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

TEMPO-oxidation of cellulose: Synthesis and characterisation of polyglucuronans

A series of pseudo amorphous cellulose samples were reacted with catalytic amounts of 2,2,6,6-tetramethyl-1-piperidine oxoammonium salt (TEMPO), sodium hypochlorite and sodium bromide in water. In all samples the primary alcohol groups were selectively oxidised into carboxyl groups, and several water-soluble polyglucuronic acid sodium salts were obtained with different molecular weights. With this reaction system, the degradation of the amorphous cellulose samples may be minimized, provided the oxidation is performed at 4°C and at constant pH 10, with controlled amounts of TEMPO and sodium hypochlorite.     

The effect of the molecular weight of chitosan nanoparticles and its application on drug delivery

Nanoparticulate drug delivery systems offer several advantages over conventional forms of dosing, with polymer nanoparticles prepared from biomaterials being good candidates for use in drug delivery. We selected fluorouracil (5FU) as a model drug because it has been suggested that chitosan might prevent the side effects induced by 5FU. We have exploited the complexation between oppositely charged macromolecules to develop a safe and efficient method of preparation of chitosan bead formulations for use as drug delivery systems. In this study, we examined the effect that the molecular weight of chitosan had on the resulting nanoparticles' properties; the initial concentration of chitosan was held constant, but its molecular weight was decreased through the action of NaNO₂. FTIR spectroscopy suggested that no structural change occurred during the depolymerization process. The diameters of the nanoparticles—determined using dynamic light scattering and TEM techniques—decreased as the value of the viscosity of molecular weight (Mv) of chitosan decreased. In addition, we prepared fluorouracil-loaded chitosan nanoparticles and characterized them using NMR spectroscopy. The encapsulation efficiency increased as the value of Mv of chitosan decreased. The particles produced using 55-kDa chitosan had a mean diameter of 70.6 nm and a 66% drug loading.     

Effect of combined gamma-irradiation and alkali treatment on cotton–cellulose

The influence of high-energy irradiation and sodium hydroxide treatment on the structure of cotton–cellulose was studied. The irradiation resulted in degradation of cellulose characterized by the decrease in the degree of polymerization (viscosimetry) and increase in the carbonyl content (FTIR, C=O stretching band at 1740 cm⁻¹). The treatment with NaOH after irradiation had no significant effect on these characteristics. However as it was shown by XRD and SEM that the transformation of the crystalline structure from cellulose I to cellulose II was observed at lower alkaline concentration when irradiation pretreatment was applied.