Novel cellulose esters derived from the levopimaric acid-maleic anhydride adduct: synthesis,characterization, and properties

Synthesis of maleated pimaric acid (MPA) cellulose esters is first reported in this work. Cellulose esterification was performed by reacting microcrystalline cellulose with monoacid chloride of MPA (MPA-Cl) in presence of pyridine as catalyst and reaction medium. The syntheses were started in a heterogeneous solid–liquid reaction medium, but as the reaction advanced, the reaction mass turned into a homogeneous solution. The effects of MPA-Cl/anhydroglucose unit molar ratio, reaction temperature, and reaction duration on the yield and degree of substitution (DS) of cellulose esters (CEs) were investigated. CEs with DS ranging from 2.6 to 2.8 were achieved at molar ratios of 5.5–6.0 after 12–16 h at 118 °C. The purified products were characterized by elemental analysis, IR and ¹³C-NMR spectroscopy, and thermogravimetric analysis. CEs are soluble or partially soluble in usual organic solvents, depending on DS. Transparent films were prepared using CE-cyclohexanone solutions.     

Hydrothermal conversion of cellulose into lactic acid with nickel catalyst

Utilization of biomass has become a major topic of research around the world. One promising aspect of utilization is production of lactic acid from carbohydrate biomass. Our previous study showed that lactic acid can be formed from glucose and cellulose by alkaline hydrothermal reactions, but the yield of lactic acid was low, particular for cellulose. In this study, an efficient method for producing lactic acid from cellulose under hydrothermal conditions with NaOH in the presence of nickel was developed. Experiments were conducted in a batch reactor at 300 °C for 1?C4 min. Results showed that nickel could promote the yield of lactic acid from cellulose. The highest yield of 34.07% was obtained by adding 0.5 mmol nickel using 2.5 M NaOH solution at 300 °C for 1 min.     

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.     

Mercerized cellulose biocomposites: a study of influence of mercerization on cellulose supramolecular structure, water retention value and tensile properties

In this study the effect of the mercerization degree on the water retention value (WRV) and tensile properties of compression molded sulphite dissolving pulp was evaluated. The pulp was treated with 9, 10, or 11 % aqueous NaOH solution for 1 h before compression molding. To study the time dependence of mercerization the pulp was treated with 12 wt% aqueous NaOH for 1, 6 or 48 h. The cellulose I and II contents of the biocomposites were determined by solid state cross polarization/magic angle spinning carbon 13 nuclear magnetic resonance (CP/MAS ¹³C NMR) spectroscopy. By spectral fitting of the C6 and C1 region the cellulose I and II content, respectively, could be determined. Mercerization decreased the total crystallinity (sum of cellulose I and cellulose II content) and it was not possible to convert all cellulose I to cellulose II in the NaOH range investigated. Neither increased the conversion significantly with 12 wt% NaOH at longer treatment times. The slowdown of the cellulose I conversion was suggested as being the result from the formation of cellulose II as a consequence of coalescence of anti-parallel surfaces of neighboring fibrils (Blackwell et al. in Tappi 61:71–72, 1978; Revol and Goring in J Appl Polym Sci 26:1275–1282, 1981; Okano and Sarko in J Appl Polym Sci 30:325–332, 1985). Compression molding of the partially mercerized dissolving pulps yielded biocomposites with tensile properties that could be correlated to the decrease in cellulose I content in the pulps. Mercerization introduces cellulose II and disordered cellulose and lowered the total crystallinity reflected as higher water sensitivity (higher WRV values) and poorer stiffness of the mercerized biocomposites.     

Study on the interaction between urea and cellulose by combining solid-state 13C CP/MAS NMR and extended Hückel charges

In this article, solid-state ¹³C CP/MAS NMR combined with extended Hückel charges was applied to investigate the interaction between urea and cellulose in the NaOH/urea aqueous solvent system. Direct experimental evidence was provided to support the interaction between urea and cellulose. The solid-state ¹³C CP/MAS NMR results revealed that complicated complexes are formed by urea, NaOH and cellulose in the solution. Excess urea exists in a free state, which explains why 7 wt% NaOH/12 wt% urea/81 wt% H₂O is the optimal ratio selection to dissolve cellulose. Based on the correlation in which the computed extended Hückel charge on carbon of urea is approximately inversely proportional to its ¹³C chemical shift, a possible interaction model of cellulose, NaOH and urea was proposed. Interactions exist between any two of urea, NaOH and cellulose, which results in the cellulose chain being surrounded by NaOH and urea molecules. NaOH and urea may be in the same surface layer of cellulose chains.     

NMR spectroscopic studies on the mechanism of cellulose dissolution in alkali solutions

It was considered that the dissolution of cellulose in alkali solutions is mainly due to the breakage of hydrogen bonds. As an alkali hydroxide, KOH can provide OH^? just like LiOH and NaOH; but it is well known that LiOH and NaOH can dissolve cellulose, whereas KOH can only swell cellulose. The inability of KOH to dissolve cellulose was investigated and the mechanism of cellulose dissolving in alkali solutions was proposed. The dissolution behavior of cellulose and cellobiose in LiOH, NaOH and KOH were studied by means of ¹H and ¹³C NMR as well as longitudinal relaxation times. The structure and properties of the three alkali solutions were compared. The results show that alkali share the same interaction mode with cellobiose and with the magnitude of LiOH > NaOH > KOH; the alkalis influence the structure of water also in the same order LiOH > NaOH > KOH. The different behavior of the three alkalis lies in the different structure of the cation hydration ions. Li⁺ and Na⁺ can form two hydration shells, while K⁺ can only form loose first hydration shell. The key to the alkali solution can or cannot dissolve cellulose is whether the cation hydration ions can form stable complex with cellulose or not. K⁺ cannot form stable complex with cellulose result in the KOH solution can only swell cellulose.     

Fluorescence Probe of 10-Phenyl-acridone-2-sulfonyl Chloride and Its Application for Determination of Free Aliphatic Amines in Environmental Samples by HPLC with Fluorescence Detection and APCI-MS

A simple and sensitive method for the determination of free aliphatic amines using 10-phenyl-acridone-2-sulfonyl chloride (PASC) as a labeling reagent by high-performance liquid chromatography with fluorescence detection and online mass spectrometry identification (HPLC-FLD-MS) has been developed. Derivatization conditions including reagent concentration, buffer pH, reaction time and temperature were optimized. PASC reacted with aliphatic amines at 50 °C for 4 min in aqueous acetonitrile (ACN) in the presence of sodiumtetraborate–NaOH buffer (0.10 mol L⁻¹, pH 9.0) to give high yields of PASC-amine derivatives. Derivatives exhibited intense fluorescence with an excitation maximum at λ_ex 265 nm and an emission maximum at λ_em 418 nm. The separation of derivatives was performed by a reversed-phase Hypersil BDS C8 column in combination with a gradient elution. The identification of derivatives was carried out by online post-column mass spectrometry with atmospheric pressure chemical ionization (APCI) source in positive-ion detection mode. Excellent linear responses were observed with the correlation coefficients of larger than 0.9997, and detection limits (at a signal-to-noise of 3:1) were from 3.0 to 24.3 fmol. Comparing with 10-ethyl-acridine-2-sulfonyl chloride (EASC), PASC exhibited more intense fluorescence and ultraviolet absorbance. The proposed method is sensitive and reproducible for the determination of aliphatic amines from water and soil samples.

     

The thermodynamics study on the dissolution mechanism of cellobiose in NaOH/urea aqueous solution

NaOH/urea aqueous solution is a novel, green solvent for cellulose. To explain why cellulose just be dissolved in this solvent under ?13 °C, we studied and discussed the dissolving process of cellobiose in water, urea solution, NaOH solution and NaOH/urea aqueous solution. Dissolving cellobiose in water and the urea solution absorb heat, which is an entropy-driven process. Dissolving cellobiose in NaOH solution and mixed NaOH/urea solution is exothermic, which is an enthalpy-driven process. OH^? plays an important role in the dissolving process by forming a hydrogen-bonding complex. From the thermodynamic point of view, negative entropy can well interpret why cellulose must be dissolved in cold NaOH/urea aqueous solution.     

The swelling and dissolution of cellulose crystallites in subcritical and supercritical water

The swelling and dissolution phenomena of microcrystalline cellulose (MCC) were investigated in subcritical and supercritical water. Commercial MCC was treated in water at temperatures of 250–380 °C and a pressure of 250 bar for 0.25–0.75 s. As reaction products, undissolved but depolymerised cellulose residue, short-chain cellulose precipitate, water-soluble cello-oligosaccharides and monosaccharides, as well as their degradation products, were detected. The highest yield of the cellulose II precipitate was obtained after a reaction time of 0.25 s at 360 °C. Our hypothesis was that if the crystallites were swollen, the depolymerization pattern would be that of homogeneous reaction and the cellulose Iβ to cellulose II transformation would be observed. The changes in the structure of the undissolved cellulose residue were characterised by size exclusion chromatography, wide-angle X-ray scattering and ¹³C solid-state NMR techniques. In many cases, the cellulose residue samples contained cellulose II; however, due to experimental limitations, it remains unclear whether it was formed through the swelling of crystallites or the partial readsorption of the dissolved cellulose fraction. The molar mass distributions of untreated MCC and after low intensity treatments showed a bimodal shape. After high intensity treatments the high molar mass chains disappeared which indicated a complete swelling or dissolution of the crystallites.     

Microwave Synthesis of 5-Substituted 1H-Tetrazoles Catalyzed by Bismuth Chloride in Water

Bismuth chloride was used to catalyze the [2 + 3] cycloaddition between sodium azide with aryl nitriles, aliphatic nitriles, and vinyl nitriles. A number of 5-substituted 1H-tetrazoles were synthesized in water or isopropanol/water mixtures using microwave heating. Good yields were obtained for these reactions when heated for 1 h at 120–160 °C in a 3:1 isopropanol/water mixture. A few of the less reactive nitriles required longer reaction times for good yields.     

Direct reduction of copper oxide into copper under hydrothermal conditions

A new preparation method of Cu from CuO under hydrothermal conditions was investigated. Glucose was employed as reducing agent. Results showed that CuO can be reduced easily to Cu° with glucose as reductant at 220?C250 °C with NaOH. The reaction conditions such as reaction time, reaction temperature, sodium hydroxide concentration and water filling played key roles in the purity of the products. The proposed method provides an efficient and green conversion of CuO into Cu° without an expensive and toxic reducing agent at low temperatures.     

Multi-technique surface characterization of bio-based films from sisal cellulose and its esters: a FE-SEM, μ-XPS and ToF-SIMS approach

Bio-based films were prepared from LiCl/DMAc solutions containing sisal cellulose esters (acetates, butyrates and hexanoates) with different degrees of substitution (DS 0.7–1.8) and solutions prepared with the cellulose esters and 20 wt% sisal cellulose. A novel approach for characterizing the surface morphology utilized field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and contact angle analysis. XPS and ToF-SIMS were a powerful combination while investigating both the ester group distribution on the surface and effects of cellulose content on the film. The surface coverage by ester aliphatic chains was estimated using XPS measurements. Fibrous structures were observed in the FE-SEM images of the cellulose and bio-based films, most likely because the sisal cellulose chains aggregated during dissolution in LiCl/DMAc. Therefore, the cellulose aggregates remained after the formation of the films and removal of the solvent. The XPS results indicated that the cellulose loading on the longer chain cellulose esters films (DS 1.8) increased the surface coverage by ester aliphatic chains (8.2 % for butyrate and 45 % for hexanoate). However, for the shortest ester chains, the surface coverage decreased (acetate, 42 %). The ToF-SIMS analyses of cellulose acetate and cellulose hexanoate films (DS 1.8) revealed that the cellulose ester groups were evenly distributed across the surface of the films.     

Ethenolate Transfer Reactions: A Facile Synthesis of Vinyl Esters

A simple and efficient metal‐free ethenolate transfer reaction has been elaborated in moderate‐to‐high yields from vinyl acetate. This reaction was accomplished by generation of potassium ethenolate, which was then reacted with homo and mixed anhydrides of aliphatic, aryl and heteroaryl acids, to yield the corresponding vinyl esters. The utility of thus generated vinyl esters was then probed by carrying out intramolecular Heck reactions to give isobenzofuran‐1(3H)‐one derivatives in excellent yields.     

Cellulose hydrolysis catalyzed by highly acidic lignin-derived carbonaceous catalyst synthesized via hydrothermal carbonization

Acidic carbonaceous solids were synthesized from mass pine alkali lignin via hydrothermal carbonization followed by sulfonation. Hydrothermal carbonization of lignin in the presence of acrylic acid (LAHC-SO₃H) provided many more carboxylic groups than that in the absence of acrylic acid, allowing subsequent sulfonation to produce a highly active and stable catalyst for cellulose hydrolysis in the [BMIM]Cl-H₂O solvent system. The hydrochar and catalyst were characterized using field emission scanning electron microscopy, X-ray diffractometer, X-ray photoelectron spectroscopy, thermal gravimetric analysis, Fourier transform infrared spectrometer, Brunauer–Emmett–Teller and acid–base titration. Results showed that a high acid content of 5.48 mmol/g, including carboxylic group (2.85 mmol/g), phenolic hydroxyl group (1.05 mmol/g) and sulfonic acid group (1.58 mmol/g), contributed significantly to the highly efficient hydrolysis of cellulose. Further, it was found that addition of trace water in [BMIM]Cl was favorable to cellulose hydrolysis. The highest yield (75.4%) of total reducing sugar (TRS) obtained in [BMIM]Cl-H₂O at a mass ratio of 100:1 was more than twice that (36.1%) achieved in [BMIM]Cl without water; the corresponding reaction conditions were 50 mg of microcrystalline cellulose, 30 mg of catalyst, 1.0 g of [BMIM]Cl, 10 mg of H₂O, reaction temperature of 130 °C and reaction time of 2 h. Furthermore, the TRS yield with 5 cycles for LAHC-SO₃H was higher than 68.1%, and the catalytic activity of catalyst could be fully recovered (74.0% of TRS yield) easily by regeneration.     

Evaluation of N719 amount in TiO2 films for DSSC by thermogravimetric analysis

The aim of this work is to evaluate the amount of N719 dye in TiO₂ films for DSSCs by thermogravimetric analysis coupled with mass spectrometry (TG-MS) in comparison with the traditional method based on the dye extraction in NaOH solutions. The characterization was carried out on TiO₂ films applied on FTO glasses by automatic screen printing method. For all the samples, TG-MS showed three well defined steps. The first, below 100 °C and coupled to an endothermic signal was due to water release. From 200 to about 300 °C, there was the release of CO₂ coming from decarboxylation reaction of N719. The last exothermic step was due to the combustion of organic residues. As the decarboxylation reaction occurs with release of 4 moles of CO₂ per mole of N719, it was used to determine the dye loading of the samples that resulted in the range 7?15 wt% well agreeing the relevant content of dye obtained by desorption with NaOH.     

LC Analysis of Aliphatic Primary Amines and Diamines After Derivatization with 2,6-Dimethyl-4-quinolinecarboxylic Acid N-Hydroxysuccinimide Ester

A method for sensitive simultaneous analysis of aliphatic primary amines and diamines has been developed and validated. The compounds were analyzed by reversed-phase high-performance liquid chromatography after pre-column derivatization with 2,6-dimethyl-4-quinolinecarboxylic acid N-hydroxysuccinimide ester as fluorescent probe. The derivatization reaction was performed at 50 °C for 40 min in 0.1 mol L^?1 borax buffer solution (pH 7.5). The resulting fluorophores were separated to baseline on a C₁₈ column and fluorimetrically detected at λ _ex/λ _em = 326/409 nm. Detection limits were in the range 0.50–0.02 nmol L^?1. The method was successfully used for analysis of aliphatic amines in water, human urine, and serum.     

Interactions with water of mixed acetic-fatty cellulose esters

Cellulose powder was acylated with mixtures containing acetic, fatty and acetic-fatty anhydrides to form acetic-fatty cellulose esters. The total degree of substitution (DS) of the mixed cellulose esters (MCE) ranged from 2 × 10⁻² to 2.92. MCE were characterized by their interactions with water. Static contact angles with water were measured on a regular smooth surface. The values found were dependent on the fatty acyl content and independent of the acetyl content. In the case of acetic-oleic cellulose esters, the minimum DS of the oleoyl moiety required to obtain permanent water repellency was 3 × 10⁻⁴. The microporosity of the samples may account for this exceptional hydrophobic character. Nevertheless, water vapor adsorption measurements on powder samples revealed only a limited increase in hydrophobicity of the MCE compared to cellulose acetate with the same acetyl content. It was thus demonstrated that water repellency and vapor water adsorption are not correlated.     

Online recovery of radiocesium from soil,cellulose and plant samples by supercritical fluid extraction employing crown ethers and calix-crown derivatives as extractants

Two crown ethers (CEs) viz. dibenzo18crown6, and dibenzo12crown7 and three calix-crown derivatives viz. (octyloxy)calix[4]arene-mono-crown-6 (CMC), calix[4]arene-bis(o-benzocrown-6) (CBC), and calix[4]arene-bis(naphthocrown-6) (CNC) were evaluated for the recovery of ¹³⁷Cs from synthetic soil, cellulose (tissue paper), and plant samples by supercritical fluid extraction (SFE) route. CEs showed poor extraction of ¹³⁷Cs from soil matrix. SFE experiments using 1 × 10^?3 M solutions of CMC, CBC and CNC in acetonitrile at 3 M HNO₃ as modifiers displayed better extraction of ¹³⁷Cs, viz. 21(±2) % (CMC), 16.5(±3) % (CBC), and 4(±1) % (CNC). It was not possible to recover ¹³⁷Cs quantitatively from soil matrix. The inefficient extraction of ¹³⁷Cs from soil matrix was attributed to its incorporation into the interstitial sites. Experiments on tissue papers using CMC showed near quantitative ¹³⁷Cs recovery. On the other hand, recovery from plant samples varied between 50(±5) % (for stems) and 75(±5) % (for leaves).     

Synthesis of 13C and 2H Labeled Vinyl Pyruvate and Hyperpolarization of Pyruvate

The hyperpolarization of nuclear spins has enabled unique applications in chemistry, biophysics, and particularly metabolic imaging. Parahydrogen-induced polarization (PHIP) offers a fast and cost-efficient way of hyperpolarization. Nevertheless, PHIP lags behind dynamic nuclear polarization (DNP), which is already being evaluated in clinical studies. This shortcoming is mainly due to problems in the synthesis of the corresponding PHIP precursor molecules. The most widely used DNP tracer in clinical studies, particularly for the detection of prostate cancer, is 1-¹³C-pyruvate. The ideal derivative for PHIP is the deuterated vinyl ester because the spin physics allows for 100 % polarization. Unfortunately, there is no efficient synthesis for vinyl esters of β-ketocarboxylic acids in general and pyruvate in particular. Here, we present an efficient new method for the preparation of vinyl esters, including ¹³C labeled, fully deuterated vinyl pyruvate using a palladium-catalyzed procedure. Using 50 % enriched parahydrogen and mild reaction conditions, a ¹³C polarization of 12 % was readily achieved; 36 % are expected with 100 % pH₂. Higher polarization values can be potentially achieved with optimized reaction conditions.     

Synthesis,isolation and characterization of methyl levulinate from cellulose catalyzed by extremely low concentration acid

A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition (180–210 °C) catalyzed by extremely low concentration sulfuric acid (≤0.01 mol/L) and the product isolation were developed in this study. Effects of different process variables towards the catalytic performance were performed as a function of reaction time. The results indicated that sulfuric acid concentration, temperature and initial cellulose concentration had significant effects on the synthesis of methyl levulinate. An optimized yield of around 50% was achieved at 210 °C for 120 min with sulfuric acid concentration of 0.01 mol/L and initial cellulose concentration below 100 g/L. The resulting product mixture was isolated by a distillation technique that combines an atmospheric distillation with a vacuum distillation where n-dodecane was added to help distill the heavy fraction. The light fraction including mainly methanol could be reused as the reaction medium without any substantial change in the yield of methyl levulinate. The chemical composition and structural of lower heavy fraction were characterized by GC/MS, FTIR, ¹H-NMR and ¹³C-NMR techniques. Methyl levulinate was found to be a major ingredient of lower heavy fraction with the content over 96%. This pathway is efficient, environmentally benign and economical for the production of pure levulinate esters from cellulose.