Replacing calcium with ammonium counterion in lignosulfonates from paper mills affects their molecular properties and bioactivity (original) (raw)
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Scientific Reports, 2021
Lignosulfonate (LS) is a by-product obtained during sulfite pulping process and is commonly used as a growth enhancer in plant growth. However, the underlying growth promoting mechanism of LS on shoot growth remains largely unknown. Hence, this study was undertaken to determine the potential application of eco-friendly ion-chelated LS complex [sodium LS (NaLS) and calcium LS (CaLS)] to enhance recalcitrant indica rice MR 219 shoot growth and to elucidate its underlying growth promoting mechanisms. In this study, the shoot apex of MR 219 rice was grown on Murashige and Skoog medium supplemented with different ion chelated LS complex (NaLS and CaLS) at 100, 200, 300 and 400 mg/L The NaLS was shown to be a better shoot growth enhancer as compared to CaLS, with optimum concentration of 300 mg/L. Subsequent comparative proteomic analysis revealed an increase of photosynthesis-related proteins [photosystem II (PSII) CP43 reaction center protein, photosystem I (PSI) iron-sulfur center, PSI...
Agronomy, 2019
The main aim of this study is to identify and investigate specific humates (Hs) as potential biostimulants. Five specialty lignosulfonates (LS1-5), one commercial leonardite-humate (PH), and one commercial lignosulfonate (LH), were analyzed for their carbon, nitrogen, and sulfur contents, and the distribution of functional groups using Fourier transform infrared (FTIR) and Raman spectroscopies. Hs were further supplied for two days to Zea mays L. in hydroponics to test their capacity to trigger changes in physiological target-responses. LS1, LS2, LS3, and LS5 determined the most pronounced effects on plant growth and accumulation of proteins and phenolics, perhaps because of their chemical and spectroscopic features. Root growth was more increased (+51-140%) than leaf growth (+5-35%). This effect was ascribed to higher stimulation of N metabolism in roots according to the increased activity of N-assimilation enzymes (GS and GOGAT) and high consumption of sugars for energy-dependent processes. Increased values of RuBisCO, SPAD (Soil Plant Analysis Development values), and leaf sugar accumulation refer to enhanced photosynthesis attributed to Hs. We conclude that Hs tested in this study functioned as biostimulants, but the specialty lignosulfonates were more efficient in this role, possibly because of the type of starting material and process used for their production, which may have influenced their chemical properties.
HortScience
Ammonium lignosulfonate (ALS) is a liquid waste by-product of pulp and paper industry that may be a source of organic fertilizer. Four plots each of tomato, pepper, broccoli, and corn were set up in a randomized block design on the AAFC-SCPFRC farm in the Spring 1998. Treatments were untreated control, 0.5% (v/w) ALS, and 1% (v/w) ALS. Soil samples were taken at 0, 2, 4, 8, and 22 weeks after amendment incorporation and analyzed for pH, microbial population, and water soluble ions. Soil temperature was measured at 8-cm depth. Leaf chlorophyll content was measured at four sampling dates. Tomato and pepper fruit were evaluated for symptoms of diseases. Soil temperature in 0.5% and 1.% ALS treatments were 2 and 7 °C warmer, respectively, than the control. Soil pH was lower in ALS-treated plots. 1% ALS caused more than 10-fold increase in bacterial population. Fungal populations in both 0.5% and 1% ALS treatments were 10- to 100-fold higher than control soil and continued to be higher t...
Planta, 1999
The composition of suberin and lignin in endodermal cell walls (ECWs) and in rhizodermal/hypodermal cell walls (RHCWs) of developing primary maize (Zea mays L.) roots was analysed after depolymerisation of enzymatically isolated cell wall material. Absolute suberin amounts related to root length significantly increased from primary ECWs (Casparian strips) to secondary ECWs (suberin lamella). During further maturation of the endodermis, reaching the final tertiary developmental state characterised by the deposition of lignified secondary cell walls (u-shaped cell wall deposits), suberin amounts remained constant. Absolute amounts of lignin related to root length constantly increased throughout the change from primary to tertiary ECWs. The suberin of Casparian strips contained high amounts of carboxylic and 2-hydroxy acids, and differed substantially from the suberin of secondary and tertiary ECWs, which was dominated by high contents of ω-hydroxycarboxylic and 1,ω-dicarboxylic acids. Furthermore, the chain-length distribution of suberin monomers in primary ECWs ranged from C16 to C24, whereas in secondary and tertiary ECWs a shift towards higher chain lengths (C16 to C28) was observed. The lignin composition of Casparian strips (primary ECWs) showed a high syringyl content and was similar to lignin in secondary cell walls of the tertiary ECWs, whereas lignin in secondary ECWs contained higher amounts of p-hydroxyphenyl units. The suberin and lignin compositions of RHCWs rarely changed with increasing root age. However, compared to the suberin in ECWs, where C16 and C18 were the most prominent chain lengths, the suberin of RHCWs was dominated by the higher chain lengths (C24 and C26). The composition of RHCW lignin was similar to that of secondary-ECW lignin. Using lignin-specific antibodies, lignin epitopes were indeed found to be located in the Casparian strip. Surprisingly, the mature suberin layers of tertiary ECWs contained comparable amounts of lignin-like epitopes.
Sodium Lignosulfonate Effect on Physiological Traits of Cucumis sativus L. Seedlings
Agriculture
The application of pulp and paper mill sludge to agricultural soils is commonly considered as a strategy to improve soil properties, promote plant growth, and reduce the demand for costly chemical fertilization. The aim of this study was to evaluate if sodium lignosulfonate (sLS), one of the sludges of pulp production, may affect the biomass production, the respiration (R) and net CO2 assimilation rate (An) at the leaf level, and the content and accumulation of trace elements in the leaves of cucumbers grown under a sufficient nutrient supply or soil nutrient deficit. A pot culture experiment was conducted using sLS application rates of 0, 1.0, 2.5, 5.0, and 10 vol% to sandy loam soil. The decline in nutrient availability caused an increase in the R/An ratio and dramatically depressed biomass accumulation. The leaf Fe, Ni, Cr, Co, Al, and Pb contents were lower under low nutrient availability than under sufficient nutrient supply. Although sLS was not very effective in lessening the...
Background and Aims Lignin of lignocellulosic residues from biomass for energy can be exploited in sustainable agriculture as plant stimulants. Lignin mono-mers or their microbial bioproducts are mainly responsible for the plant growth promotion exerted by humic matter in soil. The aim of this work was to verify the humic-like bioactivity of water-soluble lignin isolated from biomass for energy towards plant growth and relate the biostimulation to the lignin molecular structure. Methods Two water-soluble lignins isolated from giant reed (AD) and miscanthus (MG) were characterized for molecular composition by 1 H and 31 P 1D-, 13 C-1 H 2D-, DOSY-NMR spectroscopy and for conformational structure by size-exclusion chromatography. The effect of different aqueous concentrations of lignin on germination of maize seeds and growth of maize plantlets was assessed in growth-chamber experiments. Results Both lignins showed humic-like supramolecu-lar structures, but different conformational stability and molecular composition. Their largest bioactivity was revealed at 10 and 50 ppm of lignin organic carbon and both significantly increased length of radicles, lateral seminal roots, and coleoptiles of maize seedlings, as well as total shoot and root dry weights and root length of maize plantlets. However, differences in AD and MG bioactivity were attributed to their conformational sta-bilities and content of amphiphilic molecules, which may control both the adhesion to plant roots and the release of bioactive molecules upon interactions with plant-exuded organic acids. Conclusions The humic-like bioactivity of water-soluble lignins indicated that lignocellulosic residues from energy crops may be profitably recycled in agriculture as effective plant growth promoters, thereby increasing the economic and environmental sustainability of energy production from non-food biomasses. Keywords Plant growth promoters. Water-soluble lignins. Humic-like matter. Biomass for energy. Maize seed germination and growth. NMR. HPSEC
Mapping of the Hydrophobic Composition of Lignosulfonates
ACS Sustainable Chemistry & Engineering
Lignosulfonates are industrial biorefinery products that are characterized by significant variability and heterogeneity in their structural composition. Typically, they exhibit high dispersities in molar mass (molar mass distributionMMD) and in functionalities (functionality-type distributionFTD), which crucially affect their material usage. In terms of FTD, state-of-the-art lignin analytics still rely mainly on the determination of functional group contents, which are statistical averages with limited explanatory power. In contrast, our online hydrophobic interaction chromatography−size-exclusion chromatography 2D-LC approach combines the determination of both MMD and FTD in a single measurement to provide a comprehensive picture of the characteristic composition of industrial lignosulfonatesinformation hitherto inaccessible by state-of-the-art lignin analytics. In this way, the complex interrelationships between these two important structural parameters can be studied in an unprecedented manner. In this study, we reveal the considerable differences in terms of hydrophobic composition and its dispersity present in a range of different industrial lignosulfonatesdata desperately needed in tailoring and refining of lignosulfonate composition for material usage.
Journal of Applied Polymer Science, 2006
We studied the enhancement of lignin reactivity in an alkaline medium, using sodium hydroxide in a microreactor set. The chemical composition and structural characterization of the reacted lignosulfonate in terms of the phenolic hydroxyl groups, aromatic protons, weight-average molecular weight, number-average molecular weight, and lignosulfonate content of all reacted lignins were determined. The techniques that we used were ultraviolet spectroscopy, proton nuclear magnetic resonance spectroscopy, and aqueous gel permeation chromatography. Using response surface methodology, we studied how the temperature and reaction time affected the lignin properties. The reaction conditions were temperatures between 116 and 1808C and reaction times between 18 and 103 min. Modeled response surfaces showed that the two factors affected the lignin properties within the studied ranges. The phenolic hydroxyl groups, aromatic protons, and lignosulfonate content increased when the severity of the treatment increased. The weight-average molecular weight, number-average molecular weight, and solid yield (%) decreased when the severity of the treatment increased. The reactivity of the modified lignins was studied with a formaldehyde reactivity test: more severe conditions produced greater improvements in the formaldehyde reactivity.
Molecules, 2015
The molecular composition of water-soluble lignins isolated from four non-food bioenergy crops (cardoon CAR, eucalyptus EUC, and two black poplars RIP and LIM) was characterized in detail, and their potential bioactivity towards maize germination and early growth evaluated. Lignins were found to not affect seed germination rates, but stimulated the maize seedling development, though to a different extent. RIP promoted root elongation, while CAR only stimulated the length of lateral seminal roots and coleoptile, and LIM improved only the coleoptile development. The most significant bioactivity of CAR was related to its large content of aliphatic OH groups, CO carbons and lowest hydrophobicity, as assessed by 31 P-NMR and 13 C-CPMAS-NMR spectroscopies. Less bioactive RIP and LIM lignins were similar in composition, but their stimulation of maize seedling was different. This was accounted to their diverse content of aliphatic OH groups and Sand G-type molecules. The poorest bioactivity of the EUC lignin was attributed to its smallest content of aliphatic OH groups and largest hydrophobicity. Both these features may be conducive of a EUC conformational structure tight enough to prevent its alteration by organic acids exuded from vegetal tissues. Conversely the more labile conformational arrangements of the other more hydrophilic lignin extracts promoted their bioactivity by releasing biologically active molecules upon the action of exuded organic acids. Our findings indicate that water-soluble lignins from non-food crops may be effectively used as plant biostimulants, thus contributing to increase the economic and ecological liability of bio-based industries.
Springer eBooks, 2016
A high-performance liquid chromatography coupled with quadrupole tandem time-of-flight mass (HPLC-QTOF-MS) and ultraviolet spectrometry (HPLC-UV) was established for simultaneous qualitative and quantitative analysis of the major chemical constituents in Caulis Trachelospermi, respectively. The analysis was performed on an Agilent Zorbax Eclipse Plus C18 column (4.6 mm × 150 mm, 5 μm) using a binary gradient system of water and methanol, with ultraviolet absorption at 230 nm. Based on high-resolution ESI-MS/MS fragmentation behaviors of the reference standards, the characteristic cleavage patterns of lignano-9, 9'-lactones and lignano-8'-hydroxy-9, 9'-lactones were obtained. The results demonstrated that the characteristic fragmentation patterns are valuable for identifying and differentiating lignano-9,9'-lactones and lignano-8'-hydroxy-9,9'-lactones. As such, a total of 25 compounds in Caulis Trachelospermi were unambiguously or tentatively identified via comparisons with reference standards or literature. In addition, 14 dibenzylbutyrolatone lignans were simultaneously quantified in Caulis Trachelospermi by HPLC-UV method. The method is suitable for the qualitative and quantitative analyses of dibenzylbutyrolatone lignans in Caulis Trachelospermi.