GREEN CHEMISTRY
·
2023
·Vol. 25
·期 11
·4469-4481
·
IF 9.8
Pengcheng Liu,Yuanlong Guo,Gu Guo,Lei Dai,Gang Hu,Haibo Xie
In this work, a series of new lignin-graft copolymers were successfully prepared through enzymatic hydrolytic lignin (EHL)-initiated ring-opening alternating copolymerization of 3,4-dihydrocoumarin (DHC) and epoxides (EPO) through organocatalysis. A series of EPOs, including styrene oxide (SO), propylene oxide (PO), cyclohexane oxide (CHO) and lignin-derived-2-(2-methoxy-4-methyl-phenoxy) (MPO), together with DHC, were selected as model compounds to prepare EHL-g-P(DHC-alt-EPO), demonstrating the tailor-made potential of this synthetic protocol. The reaction conditions were optimized and the structures and thermal properties of EHL-g-P(DHC-alt-EPO) were fully elucidated by 1H, 13C and 31P NMR, FTIR spectroscopy, MALDI-TOF MS and GPC, DSC, and TGA. It was found that EHL-g-P(DHC-alt-SO) with a monomer conversion of 81.52%, DP of 3.21 and Mn of 62.9 kDa was prepared at a molar ratio of 5 : 5 : 1, 140 °C and 24 h. The UV shielding properties, antioxidant activity and biocompatibility of the as-prepared EHL-g-P(DHC-alt-EPO) was systematically evaluated. As a ‘proof of concept’ application, the potential of EHL-g-P(DHC-alt-SO) as an active ingredient in sunscreen was demonstrated, and a high sun protection factor (SPF) of 22.42 was achieved at 5 wt% dosage of EHL-g-P(DHC-alt-SO) in the cream, and the possible mechanism for the outstanding performance is also discussed.
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ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Pengpeng Deng,Feixiang Chen,Haodong Zhang,Yun Chen,Jinping Zhou
The abuse of antibiotics induces the emergence of drug-resistant bacteria, which greatly increases the difficulty of clinical treatment of infected wounds. It is urgent to design a multifunctional wound dressing independent of antibiotics. In this work, we designed multifunctional hydrogels based on lignin and cellulose in natural polymers. Lignin with antioxidant properties could reduce silver nanoparticles in situ and could also be used as a crosslinking agent to construct hydrogels between hydroxypropyl cellulose modified with phenylboric acid by a dynamic borate bond. Hydrogels have excellent properties such as self-healing, shape adaptability, biocompatibility, blood compatibility, antioxidant properties, excellent broad-spectrum antimicrobial properties, good tissue adhesion, and electrical conductivity. The tissue adhesion of hydrogels endows them with an excellent hemostasis property in a rat liver injury model. In vivo experiments demonstrated that hydrogels can maintain a moist healing environment, reduce inflammatory cell infiltration, promote M2 macrophage polarization, accelerate collagen deposition, promote the regeneration of new blood vessels, and significantly speed up the wound healing of methicillin-resistant Staphylococcus aureus (MRSA)-infected wounds. Therefore, these multifunctional hydrogels are an excellent candidate to treat multiple stages of wound healing and have a broad application prospect in the medical field.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Hanbyeol Kim,Jinho Lee,Yoonsoo Kim,Jeong-Myeong Ha,Young-Kwon Park,Dionisios G. Vlachos,Young-Woong Suh,Jungho Jae
Although there are many studies on the noble metal-based catalysts for the hydrodeoxygenation (HDO) of lignin model compounds such as phenols, HDO studies on lignin biomass pyrolysis oil are relatively scarce. Owing to its complex composition (i.e., a mixture of phenolic monomers and oligomers), the activity and stability of the catalysts for the HDO of pyrolysis oil are significantly different from those for the model compounds. In this study, the catalytic performances of typical HDO catalysts, that is, Ru, Pd, Ru-Re supported on carbon, and the effects of process parameters such as solvent, temperature, and space velocity were investigated for the real lignin pyrolysis oils in a continuous-flow trickle bed reactor system for the first time. We demonstrated that proper tuning of catalyst composition and process parameters allows for producing the deoxygenated hydrocarbon mixtures which can be used for gasoline, jet fuel, and diesel fuels. Specifically, activated carbon promoted the HDO of lignin oil more effectively than acidic supports like HZSM-5 and TiO 2 due to the weak adsorption of phenolic molecules. Among the different metals, Ru-Re supported on carbon exhibited the highest deoxygenation activity due to the synergy of the two metals. Tetrahydrofuran was the best solvent for lignin oil processing due to its high solubility and inertness to other side reactions (e.g., excess alkylation with ethanol solvent). The use of low space velocity of 0.2 h −1 and intermediate temperature of 350 °C resulted in the highest yield of the upgrade oil (∼25 wt%) simultaneously with the high level of deoxygenation (O/C < 0.04), mainly consisting of branched cycloalkanes. The causes of the catalyst deactivation and regeneration process are also discussed to provide practical significance.
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BIORESOURCE TECHNOLOGY
·
2023
·
IF 11.4
Tian-xiang Li,De-fang Zhao,Lin Li,Yang Meng,Yu-hui Xie,Dong Feng,Feng Wu,Delong Xie,Yuxin Liu,Yi Mei
The complexity of biomass components leads to significant variations in the performance of biomass-based carbon dots (CDs). To shed light on this matter, this study presents a comparative analysis of the fluorescence properties of CDs using pure cellulose, lignin, and protein as models. Three CDs showed different fluorescent properties, resulting from the structure difference and carbonization behavior in the hydrothermal. The relatively gentle thermal degradation of proteins allows the macromolecular structure of amino acids to be preserved. This preservation results in a more regular lattice structure, a larger sp 2 domain size, and N-doping, which contribute to the highest quantum yield (QY) of 8.7% of the CDs. In contrast, cellulose undergoes more severe thermal degradation with large amounts of small molecules generated, resulting in the CDs with fewer surface defects, more irregular lattice structures, and lower QY. These results provide a guideline for the design of carbon dots from different biomass.
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ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Haixu Wang,Dongyu Zhu,Weifeng Liu,Jianhua Huang,Jinhao Huang,Dongjie Yang,Xueqing Qiu
The use of lignin as feedstock to prepare lignin-containing waterborne polyurethane (LWPU) is of great significance for the sustainable development of low carbon materials. However, the utilization method and function of lignin in LWPU need to be further explored and developed. In this study, homogeneous and stable LWPU emulsions were prepared with low-molecular-weight lignin. Then, strong and tough LWPU/lignin nanocomposites were prepared by blending dialyzed alkali lignin (DAL) nanomicelles with LWPU emulsions. The well-dispersed DAL nanoparticles formed multiple hydrogen bonds with the LWPU matrix attributed to the existence of lignin in the polyurethane chain segments, which endowed the nanocomposites with excellent mechanical properties. When the total lignin content was 23.8 wt %, the tensile strength and toughness of LWPU/lignin nanocomposites reached 38.3 MPa and 173.9 MJ/m3, respectively. Benefiting from the photothermal function of lignin, the LWPU/lignin nanocomposites showed outstanding photothermal conversion ability, which was demonstrated as an excellent photothermal coating for photothermo-electric power generation. In addition, DAL nanoparticles enhanced the aging-induced self-reinforcing properties of the LWPU/lignin nanocomposites. This work represents a simple route for the preparation of high-performance waterborne polyurethane materials with high lignin content and opens up a novel value-added application of lignin in photothermal-electricity conversion coatings.
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INDUSTRIAL CROPS AND PRODUCTS
·
2023
·
IF 5.9
Yongchang Xiao,Jun Qi,Zihao Yu,Wang Zhao,Weiyong Shao,Nanhua Li,Yuling Kong,Lizi Li,Weiqi Wei
A ternary deep-eutectic solvents (DESs) which consisted of choline chloride-urea-ethanolamine (ChCl-U-EOA) was used for the pretreatment of corncob powder (CCP), and the effect of various pretreatment conditions on the pretreated substrates components and subsequent enzymatic digestion was investigated. The results indicated that under the optimum pretreatment conditions (110 ℃, 60 min, 10% solid concentration), the ChCl-U-EOA pretreatment could selectively remove ∼71.8% of lignin while retaining ∼87.7% of cellulose and ∼74.6% of hemicellulose , and the yields of glucose and xylose after enzymatic digestion reached ∼86.4% and ∼70.5%, respectively. The characterization of various pretreated substrates showed that the removal of lignin, and the fragmentation of pretreated substrates was the key factors to improve glucose/xylose yields. In addition, the lignin in the pretreated hydrolysate was collected by acid precipitation and fractionated by ethanol, and then lignin nanospheres (LNPs) with a particle size under 200 nm were fabricated via a solvent-antisolvent method.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Danyang Wang,Bo Li,Jun Ma,Ju Wang,Haoyu Wang,Wenzhuo Li
Because traditional slow-release fertilizers cannot effectively retain soil heat and moisture, their ability to increase crop yields is limited. To solve this problem, novel sprayable liquid mulch films (lignin-starch-acrylate, LSA) were prepared with a slow-release urea function, created by emulsion polymerization between lignin (extracted from papermaking waste liquor), starch, and acrylate monomers. The introduction of lignin transformed the LSA emulsion into a pseudoplastic fluid with enhanced sprayability. The presence of lignin in LSA film increased the elongation at break and lowered the Young's modulus, resulting in a film that is more easily pierced by crop seedlings and preserves the heat and moisture of the soil after seedling piercing. Experimental results showed that at a mass ratio of lignin to acrylate monomers of 3/7, the LSA mulch film had good sprayability and film-forming properties, suitable mechanical properties, and the lowest urea release rate. This optimized LSA film exhibited better soil insulation and water retention performance than other slow-release fertilizers. The contents of available soil nitrogen, including NH 4 + -N and NO 3 − -N, in soil covered with LSA film were 44.82 and 45.49% higher than those in soil covered with urea, respectively, and the corresponding cabbage yields increased by 33.73%. The results of this study provide a new method for preparing agricultural materials with urea slow-release as well as soil moisture and heat preservation functions.
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INDUSTRIAL CROPS AND PRODUCTS
·
2023
·
IF 5.9
Xinlu Liu,Xiaoqian Chen,Huiyang Bian,Shuzhen Ni,Zongquan Li,Na Liu,Menghua Qin,Fengshan Zhang
Highly hydrophobic fabrics by chelating lignin (alkali lignin, sodium lignin sulfonate and formic acid lignin) with metal ions (Fe 3+ , Fe 2+ and Cu 2+ ) were prepared with the surface wettability from superhydrophilic to highly hydrophobic. The lignin/metal chelated particles are in-situ deposited onto the fabric surface using dip-coating. Different lignin/metal ion system influenced the construction of hierarchical surface roughness and energy of fabrics greatly. Specially, the formation of homogeneous spherical particles on surface contributed to the minimal contact area of water droplets and fabric, and thus avoiding their adherence. The surface morphology results showed that the active groups of lignin is closely related with the surface roughness. It was found that the alkali (AL)/FeⅢ@cotton fabric achieved a maximum water CA value of 149.9° and a low surface energy of 1.90 mN/m. Its oil-water separation efficiency was higher than 99.9% and the resultant AL/FeⅢ@cotton fabric owned an excellent stability and suitability under harsh conditions. Collectively, this work is greatly significant for achieving the high-value utilization of lignin in wastewater treatments .
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Journal of Energy Storage
·
2023
·
IF 9.4
Yanpei Fei,Zhen Jiang,Dapeng Zhou,Fuliang Meng,Yitong Wu,Yi Xiong,Yuxia Ye,Tong Liu,Zhengdong Fei,Tairong Kuang,Mingqiang Zhong,Yanbiao Li,Feng Chen
The flexible textures are prominent candidates for wearable devices with energy storage and high sensitive sensor properties. This paper proposed a method for preparing a flexible textile supercapacitor with the displacement sensor property, which consisted of lignin hydrogel as the semi-solid electrolyte and polyaniline@carbon cloth as the flexible electrode . A series of lignin hydrogels with different cross-linking degrees, which were employed as the semi-solid electrolyte, were prepared by using kraft lignin and polyethylene glycol diglycidyl ether as a crosslinking agent. It is shown that the compressive strength (0.196 MPa) and water retention capacity (92.9 %) of the lignin-based hydrogel could be greatly improved by adjusting the cross-linking degree of the hydrogel. Furthermore, the textile supercapacitor was assembled by using polyaniline@carbon cloth as the flexible electrode with lignin hydrogel. The electrochemical tests show that the hydrogel supercapacitor has good ionic conductivity and rate capability, maintaining a high capacitance (200.3 F·g −1 ) and coulomb efficiency after 6000 cycles. Meanwhile, it shows good sensitivity and stability in both pressure and bending sensing tests, and has the potential to become a new generation of flexible materials.
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CELLULOSE
·
2023
·Vol. 30
·期 15
·9725-9739
·
IF 5.7
Lyu Yingren,Ji Hairui,Ji Xingxiang,Tian Zhongjian,Zhang Fengshan
Lignin has a UV-blocking ability because it contains phenolic and ketone functional groups. However, the lignin produced in the paper industry undergoes extreme polycondensation, resulting in an extremely dark color, which impedes its value-added application in the field of UV-blocking cosmetics. In this study, maleic acid (MA) was used as a green and recyclable reagent to pretreat an agricultural waste lignocellulosic biomass, Kenaf stalk. Lignin underwent a carboxyl esterification reaction with MA to produce light-colored dissolved lignin (DL), which was further prepared into lignin nanospheres and used in lignin-based sunscreens. The results showed that when adding 5 wt% DL-lignin nanospheres (DL-LNPs) to a sunscreen with an actual measured sun protection factor (SPF) of 7.05, the SPF of the lignin-based sunscreen increased to 63.82 far exceeding the commercially available SPF 50 sunscreens. The prepared lignin-based sunscreen had good biocompatibility when applied to human skin and did not stain the skin. The remaining neutral solid after pretreatment was made into Kenaf fibers by PFI milling for papermaking. The ring crush strength index of the paper increased from 2.81 N m/g to 3.14 N m/g when 15 wt% Kenaf fibers was added to the softwood pulp. When the additions Kenaf fibers was 5 wt%, the tensile index and tearing index of the paper increased from 8.57 N m/g and 4.68 mN m 2 /g to 9.22 N m/g and 5.48 mN m 2 /g, respectively. Therefore, this study provides a new way for the value-added utilization of Kenaf stalk lignocellulosic biomass. Graphical abstract
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高影响因子
COMPOSITES PART B-ENGINEERING
·
2021
·
IF 9.078
Shanshan Zhang,Shi-Neng Li,Qiang Wu,Qian Li,Jingda Huang,Wenzhu Li,Wenbiao Zhang,Siqun Wang
Cellulose-based film material, due to its remarkable physicochemical properties , environmentally friend and low cost, has been widely applied in many high-end areas. However, the lack of functional properties (e.g., flame resistance) except poor mechanical performance severely hinders their further applications. Herein, bamboo-based phosphorylated cellulose nanofibrils (B-PCNFs) were prepared through a simple two-step method composed of phosphorylation and mechanical grinding process. The resultant film prepared via solvent casting process shows an excellent mechanical strength of 115.9 MPa, remarkable elongation at break of 53.1%, high Young's modulus of 2.5 GPa and impressive work of fracture up to 41.8 MJ m −3 , respectively, which should be contributed to the formation of dense and homogeneous polymer networks reinforced by enhanced multiple interactions. When burned against the flame of alcohol lamp (700–800 °C), B HL -PCNF film also delivers appealing structural stability even over 25s, demonstrating a prominent flame resistance. Meanwhile, compared to original one, the peak heat release rate (PHRR) and total heat released (THR) of B HL -PCNF film produce a dramatical reduction, i.e., 87.3% and 86.6% for PHRR and THR, respectively. Based on the evolution of morphological and chemical structure , the highly improved flame resistance is strongly contributed to the synergy of phosphorus containing group and lignin, resulting in a protective layer composed of P x O y compound and carbon layer . The proposed mechanism for the enhanced flame retardant property is also declared and clarified. Thereby, this phosphorylated cellulose-based film that integrates outstanding mechanical performance and excellent intrinsically flame resistance holds promising potential candidate in practical applications, such as flame-retardant packaging materials.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2021
·
IF 6.953
Luyan Sun,Kungang Chai,Liqin Zhou,Dankui Liao,Hongbing Ji
To remove the bisphenol AF (BPAF) from aqueous solution, two different types of lignin-based aromatic porous polymers (LAPP-1 and LAPP-2) were fabricated via one-pot crosslinking of lignin with 1,4-dichloroxylene and 4,4′-bis(chloromethyl)-1,1′-biphenyl, respectively. The successful synthesis of LAPPs was confirmed by FTIR and XPS , SEM, TEM and N 2 adsorption-desorption analysis. Then, batch adsorption experiments were conducted to investigate adsorption properties toward BPAF. Based on the results, the adsorption processes were in accordance with the pseudo-second-order kinetic model and the Freundlich isotherm model, and the thermodynamic studies showed that the adsorption was a spontaneous and exothermic process. It is remarkable that LAPPs exhibited good adsorption performance in wide ranges of pH and ionic strength as well as in recycling process. Notably, compared to LAPP-1, LAPP-2 exhibited higher adsorption capacity for BPAF, which can be ascribed to its higher porosity and content of aromatic ring. Moreover, the comprehensive analysis of experimental and theoretical results indicated that the π-π interactions and pore adsorption may jointly drive the uptake process of BPAF. Considering the simple fabrication method employed and excellent BPAF adsorption performance, LAPPs provided new insights into the development of advanced lignin-based adsorbents for removal of BPAF from water.
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