A composite of AgNPs and lignin porous microspheres via in-situ reduction of Ag+ and its catalytic performance.

Despite the widespread utilization of nano silver composites in the domain of catalytic hydrogenation of aromatic pollutants in wastewater, certain challenges persist, including the excessive consumption of chemical reagents during the preparation process and the difficulty in recycling. In this study, silver ions were reduced in-situ by taking advantage of the adsorptive and reducing capacities of hydroxyls and amino groups on lignin porous microspheres (LPMs) under mild ultrasonic conditions, and lignin porous microspheres loaded with silver nanoparticles (Ag@LPMs) were conveniently prepared. Ag@LPMs had excellent catalytic and cycling performances for p-nitrophenol (4-NP), methylene blue (MB) and methyl orange (MO). The 4-NP could be completely reduced to 4-AP within 155 s under the catalysis of Ag@LPMs, with a pseudo-first-order kinetic constant of 1.28 min-1. Furthermore, Ag@LPMs could still complete the catalytic reduction of 4-NP within 10 min after five cycles. Ag@LPMs with the particle size ranging from 100 to 200 µm conferred ease of recycling, and the porous structure effectively resolved the issue of sluggish mass transfer encountered during the catalytic process. At the same time, the binding force of nano silver and LPMs obtained by ultrasonic was stronger than that of heating, so the materials prepared by ultrasonic had better cycling performance. Silver ions concentration and pH value in the preparation process affected the catalytic performance of Ag@LPMs, 50 mmol/L Ag+ and pH value of 7 turned out to be the optimization conditions.

Preparations of 25 wt% of Pyraclostrobin Nanosuspension Concentrate (SC) Using Lignosulfonate-Based Colloidal Spheres to Improve Its Thermal Storage Stability.

Improving the thermal storage stability of nanosuspension concentrate (SC) prepared from low-melting-point pesticide is a recognized problem. In this work, using pyraclostrobin as the raw material, 25 wt% of pyraclostrobin nano-SC was prepared through a water-based grinding method, and the optimal grinding conditions were obtained as follows: a grinding time of 23 h, D-3911 as dispersant and a dispersant dosage of 12 wt%. The pyraclostrobin nano-SC D90 size prepared based on this best formula was 216 nm. Adding glycerin could improve the stability of nano-SC at room temperature, but its thermal storage stability was still poor. For this problem, sodium lignosulfonate and cetyltrimethylammonium bromide (NaLS/CTAB) colloidal spheres were prepared through electrostatic and hydrophobic self-assembly and characterized. The delamination and precipitation of nano-SC can be significantly improved by adding an appropriate amount of colloidal spheres, and the nano-SC D90 size decreased from 2726 to 1023 nm after 7 days of thermal storage. Farmland experiments indicated the control efficiency of pyraclostrobin nano-SC against flowering cabbage downy mildew disease was about 30% higher than that of SC. Especially after adding the wetting agent, the effect of nano-SC could be comparable to that of commercial Kairun (currently the best pyraclostrobin formulation in the world).

Preparation, characterization, and adsorption performance of porous polyamine lignin microsphere.

In this study, a porous polyamine lignin microsphere (PPALM) was prepared through the inverse suspension polymerization combined with freeze-drying, during which sodium lignosulfonate and polyetheramine (PEA) were crosslinked with epichlorohydrin (ECH) as the cross-linker. By adjusting the amount of ECH and PEA, the optimized PPALM exhibited suitable crosslinking degree, ensuring a balance of framework flexibility and rigidity, thereby facilitating the formation of abundant and fine pores. PPALM demonstrated good mechanical properties comparable to commercial sulfonated polystyrene cationic resin, with a porosity of 61.12 % and an average pore size of 283.51 nm. The saturation adsorption capacity of PPALM for Pb2+ was measured to be 156.82 mg/g, and it remained above 120 mg/g after five cycles of regeneration. Particularly, the concentration of 50 mg/L Pb2+ solution could be reduced to 0.98 mg/L after flowing through the PPALM packed bed, indicating the great potential of PPALM for application in wastewater treatment.

Preparation of a new gel-type lignin-based cationic adsorption resin for efficient removal of Ca2+ from aqueous solutions.

Presently, most studies on modified lignin focused on the adsorption to heavy metal cations, but rarely to Ca2+ in hard water. Therefore, this work prepared a new gel-type lignin-based cationic adsorption resin (E-LSAF) through the crosslinking and curing of alkali lignin grafted by sodium sulfite sulfonated acetone to remove Ca2+ in water. Under the determined optimum synthesis conditions, E-LSAF with a highest sulfonic group content of 1.99 mmol/g was obtained. Structural and physicochemical measuring results showed E-LSAF was a gel-type resin, owning strong hydrophilicity, high mechanical strength, excellent thermal stability and acid-alkaline resistance. Adsorption results indicated the adsorption of E-LSAF to Ca2+ was well-fitted by Langmuir model, and the maximum adsorption capacity reached 45.8 mg/g. Pseudo-second-order model can describe this adsorption process well, suggesting it a chemisorption process. Dynamic column adsorption results showed E-LSAF could transform hard water into soft or even very soft water. The regeneration efficiency still maintained 80 % after 5 cycles. The adsorption mechanism was attributed to electrostatic attraction, ion exchange and complexation. This work provided a high-performance lignin-based cationic adsorption material with high adsorption capacity to Ca2+ and excellent acid-alkaline resistance, which filled the research gap of using modified sulfonated lignin to remove Ca2+ from water.

Preparation of nano disperse dyes using sulfomethylated lignin: Effects of sulfonic group contents.

The molecular simulation software was firstly applied to analyze the adsorption of sulfomethylated lignin (SAL) on dye surfaces. Then, SALs with different sulfonic group contents were prepared and characterized by FTIR, NMR, EA and GPC measurements using alkali lignin (AL) as raw materials and sodium sulfite as sulfonating agents. Next, SAL1.53 was determined to the optimum dispersant by TSI, particle size and thermal storage stability measurements, which had the smallest particle size of 173 nm and highest stability, comparable to the commercial Reax 85A lignin dispersant and basically satisfying the requirement of nano disperse dyes used in the digital printing technology. QCM, AFM and zeta potential results indicated that as the sulfonic group content of SAL increased, the adsorption mass, rigidity of the adsorbed layer, adsorption force and absolute zeta potential value all showed a gradually increasing tendency due to an enhanced hydrophilicity, and thus a decreased intermolecular agglomeration and an increased molecular chain stretching degree. A maximum was observed for SAL1.53. This research not only provided a novel approach to the preparation of high-performance lignin dispersants for nano disperse dyes, but also would broaden the high value-added industrial applications of biomass lignin into the digital printing and dyeing field.

Preparation of polyether amine-bridged lignosulfonate for utilization as a nano dye dispersant.

The long-term stability of nano disperse dye slurry is a problem in industry. In this work, high molecular-weight polyether amine-bridged lignosulfonates (PEABLs) were prepared to improve the adsorption strength of dispersants on dye surfaces, and thus the stability of nano disperse dyes. Specifically, the molecular simulation software was firstly used to analyze the adsorption of PEABL on dye surfaces. Then, PEABLs with different molecular weights were synthesized and characterized by adjusting the addition of polyether amine. Next, nano disperse dyes were prepared using PEABLs and the optimum grinding conditions were explored and obtained. Finally, PEABL3 was determined to the optimum dispersant, having a smallest particle size (168 nm) and highest stability, comparable to the commercial Reax 85A dispersant and basically satisfying the demand of nano disperse dyes required in digital transfer printing technology. Quartz crystal microbalance (QCM), atomic force microscopy (AFM) and zeta potential results showed as the molecular weight of PEABL increased, the adsorption amount, adsorbed layer rigidity, adsorption force and absolute zeta potential value all firstly increased due to the enhanced hydrophobic interaction, and then decreased due to the formation of complicated three-dimensional network structures caused by the crosslink of lignosulfonate molecules. A maximum was observed for PEABL3.

Preparation of uniform lignosulfonate-based colloidal spheres for UV-absorbing thermoplastics.

Lignosulfonate-based colloidal spheres were prepared from sodium lignosulfonate and cetyltrimethylammonium bromide (NaLS/CTAB) complex through electrostatic and hydrophobic self-assembly. Due to the stronger hydrophobicity and UV-blocking performance, NaLS/CTAB colloids were easier to be blended with HDPE than lignosulfonate, and therefore applied to UV-absorbing thermoplastics. Results showed NaLS/CTAB colloidal spheres had a particle size of 160 nm with a polydispersity index of 0.081. NaLS/CTAB molecules started to form spheres at critical water content of 64 vol% when the initial concentration of NaLS/CTAB in EtOH was 0.5 mg/cm3 and the obtaining of colloids was completed at a water content of 90 vol%. The size and polydispersity of spheres were well controlled by adjusting initial concentrations of NaLS/CTAB in EtOH. Since NaLS/CTAB colloidal spheres retained phenylpropane units and phenolic hydroxyl groups of NaLS, NaLS/CTAB/HDPE composites displayed excellent UV-absorbing properties. Meanwhile, the mechanical property of NaLS/CTAB/HDPE composites was also superior to that of frequently-used CaCO3/HDPE materials in industry, reaching the requirement of industrial uses. However, too high additions would result in the increased agglomeration of NaLS/CTAB spheres in HDPE, and thus the deteriorated mechanical property. Additionally, the added spheres played a role of "ball", which caused the decreased viscosity, improved flowability and processability of composites.

Natural variation in WHITE-CORE RATE 1 regulates redox homeostasis in rice endosperm to affect grain quality.

Grain chalkiness reduces the quality of rice (Oryza sativa) and is a highly undesirable trait for breeding and marketing. However, the underlying molecular cause of chalkiness remains largely unknown. Here, we cloned the F-box gene WHITE-CORE RATE 1 (WCR1), which negatively regulates grain chalkiness and improves grain quality in rice. A functional A/G variation in the promoter region of WCR1 generates the alleles WCR1A and WCR1G, which originated from tropical japonica and wild rice Oryza rufipogon, respectively. OsDOF17 is a transcriptional activator that binds to the AAAAG cis-element in the WCR1A promoter. WCR1 positively affects the transcription of the metallothionein gene MT2b and interacts with MT2b to inhibit its 26S proteasome-mediated degradation, leading to decreased reactive oxygen species production and delayed programmed cell death in rice endosperm. This, in turn, leads to reduced chalkiness. Our findings uncover a molecular mechanism underlying rice chalkiness and identify the promising natural variant WCR1A, with application potential for rice breeding.

Lignin-Based Nanoparticles: A Review on Their Preparations and Applications.

Lignin is the most abundant by-product from the pulp and paper industry as well as the second most abundant natural renewable biopolymer after cellulose on earth. In recent years, transforming unordered and complicated lignin into ordered and uniform nanoparticles has attracted wide attention due to their excellent properties such as controlled structures and sizes, better miscibility with polymers, and improved antioxidant activity. In this review, we first introduce five important technical lignin from different sources and then provide a comprehensive overview of the recent progress of preparation techniques which are involved in the fabrication of various lignin-based nanoparticles and their industrial applications in different fields such as drug delivery carriers, UV absorbents, hybrid nanocomposites, antioxidant agents, antibacterial agents, adsorbents for heavy metal ions and dyes, and anticorrosion nanofillers.

Effects of Cationic Cetyltrimethylammonium Bromide on the Aggregation Behavior of Sodium Lignosulfonate (NaLS) in Concentrated Solutions and Preparation of Uniform Lignosulfonate-Based Colloidal Spheres.

The effects of cetyltrimethylammonium bromide (CTAB) on the aggregation behavior of sodium lignosulfonate (NaLS) in concentrated solutions were investigated by rheology, conductivity, ζ-potential, surface tension, contact angle, and elemental analysis measurements. Results showed that the presence of CTAB led to increased aggregate effects and enhanced association networks due to intermolecular bridging caused by the formation of mixed aggregates containing NaLS hydrophobes and CTAB molecules at CTAB/NaLS mixing ratios (w/w) below stoichiometric mass ratio (SMR). However, further addition of CTAB resulted in the progressive disruption of network structures due to electrostatic repulsions between aggregates. There were electrostatic and hydrophobic interactions between NaLS and CTAB. The NaLS/CTAB mixing system could form regular colloidal spheres via electrostatic and hydrophobic self-assembly in an EtOH/water mixture. As the addition of CTAB increased, the ζ-potential of NaLS/CTAB colloidal spheres was decreased, and the particle size was increased. This work provides a novel approach to the value-added utilization of lignosulfonate biomass resources.

Preparation of self-dispersed lignin-based drug-loaded material and its application in avermectin nano-formulation.

In this work, the anionic and cationic lignin-based drug-loaded materials (SL/CTAB) with strong hydrophobicity were prepared by using Sodium Lignosulfonate (SL) via self-assembly. The obtained SL/CTAB was used as drug-loaded material and emulsifier to prepare avermectin nano-formulation, which can be automatically dispersed into nano drug-loaded nanospheres in water. The cold and hot storage experiments show that the physical and chemical stability of the nano-formulation is good. The nano-formulation exhibits controlled-release performance, and the cumulative release amounts range from 56.27% to 87.33% in 62 h. Meanwhile, the release rates slow down with increasing SL/CTAB dosage. After UV irradiation for 50 h, the retention rates of avermectin in the nano-formulation range from 46.67% to 63.41%, which is 2.18-2.96 times higher than commercial avermectin Emulsifiable Concentrate (EC). The experiment of simulated rainwater scour-resistance shows that the affinity of lignin-based nano-formulation to the Epipremnum aureum leaves is higher than EC formulation.

Synthesis of anti-photolysis lignin-based dispersant and its application in pesticide suspension concentrate.

In the formulation of pesticide Suspension Concentrate (SC), some photosensitive pesticides are easily decomposed in the preparation. In this study, a hindered amine modified lignosulfonate (SL-Temp) with anti-photolysis function was synthesized using 4-amino-2,2,6,6-tetramethylpiperidine (Temp) and Sodium Lignosulfonate (SL) to solve this problem. The obtained SL-Temp was used as a dispersant to prepare 5% SC of avermectin, which shows good physical stability. The decomposition rate of the avermectin in SC after accelerating hot storage is 0%, which is much lower than 6.1% when SL was used as the dispersant. After being exposed to UV irradiation for 60 hours, the highest retention rate of avermectin is 87.1% when SL-Temp was used as the dispersant, which is much higher than 73.6% when SL was used as the dispersant, and also higher than 76.3% when a small molecule antioxidant (BHT) was added to the formulation. QCM-D studies revealed that the SL-Temp adsorption layer on avermectin particles can compete to absorb partial ultraviolet rays, hinder the penetration of ultraviolet light, and scavenge the free radicals produced by photooxidation, so as to protect avermectin from degradation.

Synthesis of a Hindered Amine-Grafted Lignin-Based Emulsifier and Its Application in a Green Emulsifiable Concentrate.

4-Amion-2,2,6,6-tetramethylpiperidine (Temp) was grafted into sodium lignosulfonate (SL) to obtain hindered amine-modified lignosulfonate (SL-Temp). Then, the polymer surfactant (SL-Temp-CTAB) was prepared using cetyltrimethylammonium bromide (CTAB) and SL-Temp. Obtained SL-Temp-CTAB was used as an emulsifier to prepare a green emulsifiable concentrate (EC) of avermectin (AVM), which shows good emulsifying property and storage stability. The prepared AVM green EC can form AVM-loaded microspheres with nanometer particle size distribution after emulsification in water. After ultraviolet irradiation for 70 h, the AVM retention rate of the green EC prepared using SL-Temp-CTAB was 75.8%, which is much higher than that of commercial EC (0.4%) and the green EC prepared using unmodified SL (31.4%). Moreover, the AVM green EC prepared using SL-Temp-CTAB has slow-release performance, and the release equilibrium time is 5.3 times the commercial EC. Therefore, the newly prepared AVM green EC using a lignin-based functional emulsifier shows good antiphotolysis and slow-release performance compared to the traditional EC.

Effect of the molecular structure of lignin-based polyoxyethylene ether on enzymatic hydrolysis efficiency and kinetics of lignocelluloses.

Effect of the molecular structure of lignin-based polyoxyethylene ether (EHL-PEG) on enzymatic hydrolysis of Avicel and corn stover was investigated. With the increase of PEG contents and molecular weight of EHL-PEG, glucose yield of corn stover increased. EHL-PEG enhanced enzymatic hydrolysis of corn stover significantly at buffer pH 4.8-5.5. Glucose yield of corn stover at 20% solid content increased from 32.8% to 63.8% by adding EHL-PEG, while that with PEG4600 was 54.2%. Effect of EHL-PEG on enzymatic hydrolysis kinetics of cellulose film was studied by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). An enhancing mechanism of EHL-PEG on enzymatic hydrolysis kinetics of cellulose was proposed. Cellulase aggregates dispersed by EHL-PEG excavated extensive cavities into the surface of cellulose film, making the film become more loose and exposed. After the maximum enzymatic hydrolysis rate, the film was mainly peeled off layer by layer until equilibrium.

Lignin-based polyoxyethylene ether enhanced enzymatic hydrolysis of lignocelluloses by dispersing cellulase aggregates.

Water-soluble lignin-based polyoxyethylene ether (EHL-PEG), prepared from enzymatic hydrolysis lignin (EHL) and polyethylene glycol (PEG1000), was used to improve enzymatic hydrolysis efficiency of corn stover. The glucose yield of corn stover at 72h was increased from 16.7% to 70.1% by EHL-PEG, while increase in yield with PEG4600 alone was 52.3%. With the increase of lignin content, EHL-PEG improved enzymatic hydrolysis of microcrystalline cellulose more obvious than PEG4600. EHL-PEG could reduce at least 88% of the adsorption of cellulase on the lignin film measured by quartz crystal microbalance with dissipation monitoring (QCM-D), while reduction with PEG4600 was 43%. Cellulase aggregated at 1220nm in acetate buffer analyzed by dynamic light scattering. EHL-PEG dispersed cellulase aggregates and formed smaller aggregates with cellulase, thereby, reduced significantly nonproductive adsorption of cellulase on lignin and enhanced enzymatic hydrolysis of lignocelluloses.

Dosimetric evaluation of volumetric-modulated arc therapy (RapidArc) for primary leiomyosarcoma in the spine.

This study aims to investigate the suitability of volumetric-modulated arc therapy (VMAT) with RapidArc for primary leiomyosarcoma (LMS) in the spine, and present a new method to improve the target coverage and organs at risk (OAR) sparing. Five patients with LMS were retrospectively reviewed. The intensity-modulated radiotherapy (IMRT) with five coplanar beams (5b-IMRT) or seven coplanar beams (7b-IMRT), and VMAT using four quasi-quarter coplanar arcs (4q-VMAT) or two full coplanar arcs (2f-VMAT) were generated. Planning target volume (PTV) dose coverage, OAR dose sparing, conformity index (CI), and homogeneity index (HI) were evaluated. A hollow-cylinder model (HCM) was also used for feasible optimal beam arrangements. The mean doses to PTV were 95.2% ± 1.0%, 93.0% ± 1.0%, 97.9% ± 1.0% and 96.2% ± 1.5% for 4q-VMAT, 2f-VMAT, 5b-IMRT and 7b-IMRT respectively, while the mean maximum doses to spinal cord (SC) were 43.7 ± 0.9 Gy, 42.0 ± 0.8 Gy, 41.4 ± 1.2 Gy and 40.6 ± 1.4 Gy. Compared to 5b-IMRT, the mean doses delivered to kidneys decreased by about 35.1% (8.5 Gy), 2.5% (0.6 Gy) and 35.5% (8.6 Gy) for 4q-VMAT, 2f-VMAT, and 7b-IMRT, respectively. The CI proposed by Baltas et al. was twice as good with IMRT than with 4q-VMAT, and the numbers of monitor units were increased five- and threefold with 7b-IMRT and with 5b-IMRT compared to VMAT. The unexpected results we presented here show that VMAT technique can't achieve highly conformal treatment plans while maintaining SC sparing for LMS in the spine. An approach is proposed based on a hollow-cylinder model, but it is difficult to apply to clinical practice. In this case, VMAT is not superior to IMRT except for significant reduction in delivery time.

Reducing non-productive adsorption of cellulase and enhancing enzymatic hydrolysis of lignocelluloses by noncovalent modification of lignin with lignosulfonate.

Four fractions of one commercial sodium lignosulfonate (SXP) with different molecular weight (MW) and anionic polymers were studied to reduce non-productive adsorption of cellulase on bound lignin in a lignocellulosic substrate. SXP with higher MW had stronger blocking effect on non-productive adsorption of a commercial Trichoderma reesi cellulase cocktail (CTec2) on lignin measured by quartz crystal microgravimetry with dissipation monitoring. Linear anionic aromatic polymers have strong blocking effect, but they would also reduce CTec2 adsorption on cellulose to decrease the enzymatic activity. The copolymer of lignin and polyethylene glycol (AL-PEG1000) has strong enhancement in enzymatic hydrolysis of lignocelluloses, because it not only improves the cellulase activity to cellulose, but also blocks the non-productive cellulase adsorption on lignin. Apart from improving the cellulase activity to cellulose, the enhancements of enzymatic hydrolysis of lignocellulose by adding AL-PEG1000 and SXPs are the result of the decreased cellulase non-productive adsorption on lignin.

Investigation of aggregation and assembly of alkali lignin using iodine as a probe.

Molecular iodine has been introduced into the alkali lignin (AL) solutions to adjust the π-π aggregation, and the effect of lignin-iodine complexes on the aggregation and assembly characteristics of AL have been investigated by using fluorescence, UV-vis spectroscopy, light scattering, and viscometric techniques. Results show that AL form π-π aggregates (i.e., J-aggregates) in THF driven by the π-π interaction of the aromatic groups in AL, and the π-π aggregates undergo disaggregation in THF-I(2) media because of the formation of lignin-iodine charge-transfer complexes. By using iodine as a probe to investigate the aggregation behaviors and assembly characteristics, it is estimated that about 18 mol % aromatic groups of AL form π-π aggregates in AL molecular aggregates. When molecular iodine is introduced into the AL solutions, lignin-iodine complexes occur with charge-transfer transition from HOMO of the aromatic groups of AL to the LUMO of iodine. The formation of lignin-iodine complexes reduces the affinity of the aromatic groups approaching each other due to the electrostatic repulsion and then eliminates the π-π interaction of the aromatic groups. The disaggregation of the π-π aggregates brings a dissociation behavior of AL chains and a pronounced molecular expansion. This dissociation behavior and molecular expansion of AL in the dipping solutions induce a decrease in the adsorbed amount and an increase in the adsorption rate, when AL is transferred from the dipping solution to the self-assembled adsorbed films. Consequently, the adsorption behavior of AL can be controlled by adjusting the π-π aggregation. Above observations give insight into the occurrence of J-aggregation of the aromatic groups in the AL molecular aggregates and the disaggregation mechanism of AL aggregates induced by the lignin-iodine complexes for the first time. The understanding can provide an academic instruction in the efficient utilization of the alkali lignin from the waste liquor and also leads to further development in expanding functionalities of the aromatic compounds through manipulation of the π-π aggregation.

Aggregation behavior of sodium lignosulfonate in water solution.

Lignosulfonate is a type of macromolecular surfactant widely used as interfacial additive in various industrial fields and it is produced during chemical pulping process. In this paper, we present a new effective method for measurement of the critical aggregation concentration (CAC) of sodium lignosulfonate (SL) in water solution, with which a value of 0.38 g L(-1) was obtained. Through the determination of CAC and observation by DLS, the state and dynamics of the formation of the SL micelles were disclosed. The results showed that SL was the state of individual molecules when its mass concentration was less than CAC; the individual SL molecules started to aggregate above CAC and thus micelles formed and grew with increasing SL concentration. The SL solution was quickly frozen and the structures of SL molecules or micelles were observed by ESEM, revealing that the spherical micelles were the main form of SL in the solution. Based on the results, the spherical hollow vesicular structure is proposed as a model of the aggregated micelles of SL in the solution.