Catalysis Science & Technology
·
2020
·Vol. 10
·期 22
·7555-7565
·
IF 5.721
Chenlin Ji,Suyun Jie,Pierre Braunstein,Bo-Geng Li
Aliphatic polyesters are a class of biorenewable, biocompatible, and biodegradable materials. The ring-opening polymerization (ROP) of lactones is one of the most powerful methods to access these materials. A novel series of benzoheterocyclic urea catalysts has been synthesized and characterized. When employed in the ROP of δ-valerolactone (δ-VL) in combination with 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), a fast and “living”/controlled feature was observed in both solvent-free polymerization and solution polymerization, which was proved by kinetic and chain extension experiments. With benzyl alcohol as an initiator, polyvalerolactones (PVLs) were obtained with different molecular weights and narrow molecular weight distributions. In addition, the PVLs with different topological structures were prepared by varying the initiators. The structure and thermal properties of resulting polymers were determined by NMR, GPC and DSC analyses. A possible mechanism was also proposed on the basis of NMR analysis.
研究领域:
材料科学
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
Reaction Chemistry & Engineering
·
2020
·Vol. 5
·期 3
·531-538
·
IF 3.441
Xiaolin Pei,Jiapao Wang,Haoteng Zheng,Pengfei Cheng,Yifeng Wu,Anming Wang,Weike Su
D-(−)-Pantolactone (D-PL) is the key chiral intermediate used to synthesize calcium D-pantothenate. In a previous study, a conjugated polyketone reductase (CduCPR) was discovered to efficiently catalyse ketopantolactone (KPL) to D-PL with a high stereoselectivity. Nevertheless, this method was limited due to the expensive coenzyme, nicotinamide adenine dinucleotide phosphate hydrate (NADPH), and the poor stability of substrate KPL in pure aqueous buffer. Here, to overcome these problems, we developed a whole-cell biotransformation process to produce D-PL in a biphasic reaction system. Recombinant CduCPR and glucose dehydrogenase (BsuGDH) were co-expressed in Escherichia coli to simultaneously achieve the synthesis of D-PL and the regeneration of NADPH. The biphasic reaction system contained 15% dichloromethane (v/v) which significantly inhibited the undesirable hydrolysis of KPL. Approximately, 2.8% of 100 mM KPL was spontaneously hydrolysed to ketopantoic acid in the biphasic system, which was lower than 54% of pure aqueous buffer. The biphasic reaction system was optimized and scaled up to prepare D-PL. In a fed-batch biphasic reaction, the substrate KPL was continuously fed into the reactor after a batch reaction. The D-PL concentration reached 0.77 mol L−1 in the reaction mixture at 7 h, and its enantiomeric excess was 99%. This study presented an alternative method to asymmetrically synthesize enantiopure D-PL for further industrial application.
研究领域:
生物技术
·
生物化学
·
酶学
✓ 已验证
DOI
高影响因子
Polymer Chemistry
·
2014
·Vol. 5
·期 8
·3098-3106
·
IF 5.368
Yu Jin,Yufeng Ji,Xiaojiang He,Suli Kan,Haidong Xia,Binqi Liang,Jia Chen,Hao Wu,Kai Guo,Zhenjiang Li
o-Benzenedisulfonimide (OBS) was demonstrated for the first time to be a safe, recyclable, and water-tolerant Brønsted acidic catalyst for the ring-opening polymerization (ROP) of δ-valerolactone and ε-caprolactone using benzyl alcohol as the initiator. The polymerizations proceeded to afford poly(δ-valerolactone) and poly(ε-caprolactone) with controlled molecular weights and narrow polydispersities. The kinetics and chain extension experiments were carried out to confirm the controlled/living fashion of the polymerizations. In addition, 1H NMR and MALDI-TOF MS measurements strongly indicated that the initiator residue was incorporated into the obtained polymers. Furthermore, well-defined poly(δ-valerolactone)-block-poly(ε-caprolactone) has been successfully synthesized via OBS-catalyzed ROP.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子
ChemCatChem
·
2015
·Vol. 7
·期 8
·1372-1379
·
IF 4.556
Xing Tang,Xianhai Zeng,Zheng Li,Weifeng Li,Yetao Jiang,Lei Hu,Shijie Liu,Yong Sun,Lu Lin
Graphical In situ generated catalyst system: HCl/ZrO(OH) 2 catalysts are prepared in situ by the autonomous decomposition of ZrOCl 2 ⋅ 8 H 2 O in levulinic acid (LA)/2-butanol solution. The esterification of LA was catalyzed in tandem with hydrocyclization to γ-valerolactone (GVL) by Meerwein–Ponndorf–Verley reduction. This is the first report of HCl/ZrO(OH) 2 catalysts prepared in situ by the autonomous decomposition of ZrOCl 2 ⋅ 8 H 2 O in levulinic acid (LA)/2-butanol solution, which catalyzed the esterification of LA in tandem with hydrocyclization to γ-valerolactone (GVL) by Meerwein–Ponndorf–Verley (MPV) reduction without the use of external H 2 . A maximum GVL yield of 92.4 % from neat LA and a GVL formation rate of 1092.2 μmol g −1 min −1 were achieved in 2-butanol at 240 °C in 2 h. The in situ generated ZrO(OH) 2 was characterized comprehensively and its unexpected catalytic efficiency was attributed mainly to its extremely high surface area. A crude LA stream from the acid hydrolysis of cellulose was extracted into 2-butanol and subjected to this catalyst system to give a GVL yield of 82.0 % even in the presence of humins.
研究领域:
化学工程
·
可再生能源
·
催化化学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2025
·
IF 5.2
Zi-Quan Wang,Ya-Peng Du,Xiao-Ping Zheng,Yu Chai,Yu-Cang Zhang,Yan-Zhen Zheng
The direct conversion of raw lignocellulosic waste into specialty chemicals such as levulinic acid (LA) has the potential to significantly enhance biorefinery profitability. Here, we demonstrated that incorporating γ-valerolactone (GVL) as a co-solvent during the SO 3 H-functionalized ionic liquid-catalyzed conversion of bagasse in water markedly enhanced reaction rates and catalytic activity, achieving a LA yield as high as 76.1 % with a 1:1 vol ratio of GVL to water. This catalytic system also effectively converted other lignocellulosic waste to LA. Reaction constants and activation energies for the bagasse dehydration process to LA were obtained. Comprehensive characterization via Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) elucidated significant changes in functional groups, surface morphology, and crystallinity index of solid residues over extended reaction times. Notably, hemicellulose and cellulose were converted within 4 h, with lignin remaining in the solid residues and forming by-products after prolonged reaction times. This efficient one-pot conversion method showed promise as a sustainable approach to transform agricultural waste into LA, offering new opportunities for eco-friendly resource utilization.
研究领域:
生物化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2022
·Vol. 12
·期 26
·16942-16954
·
IF 4.036
Yawei Zhan,Meixin Wang,Tengfei Ma,Zhiqiang Li
In this study, the effect of the γ-valerolactone (GVL)/H2O pretreatment system on bamboo (Neosinocalamus affinis) for enzymatic hydrolysis and ethanol fermentation was investigated. The performance characterization of the pretreated bamboo substrates, including the chemical composition, the structural characteristics, and the ability to produce bioethanol, were evaluated. The recovered substrates were enzymatically hydrolyzed for 48 h and then fermented to bioethanol. For the cellulose in the raw bamboo material, the highest cellulose-to-glucose conversion yield (CGCY) was achieved at 140 °C for 2 h with GVL : H2O = 8 : 2, which was 73.39%, and the cellulose-to-ethanol conversion yield (CECY) was 67.00%. This indicated that 183.5 kg of bioethanol could be produced per ton of bamboo, which was 9.71-folds higher than that directly converted from the untreated raw bamboo powder. Under these conditions, 50.60% of the active lignin can be recovered and be used as a wood-derived feedstock for further high-valued utilization. Meanwhile, the maximum concentration of fermentation inhibitors formed after pretreatment was about 140.9 mmol L−1, and had weak inhibition to the subsequent reaction. It has been shown that the cellulose could be effectively separated from bamboo and converted into bioethanol through the GVL/H2O pretreatment system.
研究领域:
生物能源
·
植物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Ying Zhu,Furui Hu,Zi Yu,Yongxin Liang,Tao Gan,Huayu Hu,Zuqiang Huang,Yanjuan Zhang
The activation of reaction system for high-efficiency hydrogenation of levulinic acid (LA) into γ-valerolactone (GVL) is significant for sustainable development of biomass. Herein, based on a strategy of tourmaline (TM)-activated aqueous-phase system, a Cu-Ni/ZrO 2 @TM/C catalyst was facilely constructed by a totally solid-phase method. Cu-Ni/ZrO 2 @TM/C exhibited outstanding catalytic performance, benefiting from the spontaneous polarization and far-infrared radiation characteristics of tourmaline and the strong metal–metal and metal–support interactions. Under the optimum reaction conditions of 180 °C, 150 min, and 1.5 MPa H 2 , 100.0 % of LA conversion and 93.0 % of GVL yield were achieved. A variety of tests and theoretical calculations confirm that tourmaline with spontaneously polarized electric field and far-infrared radiation can break intermolecular hydrogen bonds to form small water clusters for activating aqueous-phase environment, facilitating the transport of active species as well as greatly reducing the hydrogenation barrier. The activating water effect of tourmaline, the acid sites and oxygen vacancies of ZrO 2 , and the alloying structure of Cu-Ni bimetal can synergistically benefit the transport of active species for reinforcing water-assisted proton hopping. Moreover, a reasonable tourmaline-activated aqueous-phase system was proposed to explain the enhanced aqueous hydrogenation of LA. This study innovatively illuminates the construction of functional non-precious metal catalysts for efficient aqueous-phase hydrogenation of biomass-derived chemicals.
研究领域:
化学工程
·
催化科学
·
可再生资源转化
✓ 已验证
产品关联
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2024
·Vol. 18
·期 11
·1-14
·
IF 4.3
Mo Shuhua,Zheng Yao,Gong Jianyu,Lu Minsheng
The efficient fractionation and recovery of monosaccharides (xylose and glucose) from lignocellulosic biomass facilitates subsequent sugar-based derivative production. This study introduces a one-pot γ -valerolactone/ CuCl 2 biphasic pretreatment system (100-mmol·L -1 CuCl 2 , 180 °C, 60 min) capable of achieving removal rates of 92.25% and 90.64% for xylan and lignin, respectively, while retaining 83.88% of cellulose. Compared to other metal chlorides (NaCl, LiCl, FeCl 3 , and AlCl 3 ), the γ -valerolactone/CuCl 2 system recovered 121.2 mg·(g eucalyptus) -1 of xylose and 55.96 mg·(g eucalyptus) -1 of glucose during the pretreatment stage and 339.2 mg·(g eucalyptus) -1 of glucose during the enzymatic hydrolysis stage (90.78% of glucose yield), achieving a total monosaccharide recovery of 86.31%. In addition, the recovery of γ -valerolactone was 79.33%, exhibiting minimal changes relative to the pretreatment performance. The method proposed in this study allows a high total monosaccharides recovery and a circular economy-oriented pretreatment approach, offering a viable pathway for biorefinery.
研究领域:
生物工程
·
可再生资源技术
✓ 已验证
DOI
高影响因子
BIORESOURCE TECHNOLOGY
·
2012
·
IF 4.98
Yan Zhao,Yao Fu,Qing-Xiang Guo
In the present study, γ-valerolactone (GVL) is firstly reported to be converted into aromatic hydrocarbons through catalytic pyrolysis . The catalysts and reaction conditions are both critical in maximizing the hydrocarbon selectivity . Four zeolites , i.e. MCM-41, β-zeolite, ZSM-5 and HZSM-5 were tested in this work, among which HZSM-5 (Si/Al = 25) was found to be the most effective catalyst in both reactivity and selectivity. Under the reaction temperature of 500 °C, the highest carbon yield of 56.71% of aromatics was achieved from GVL with HZSM-5 (Si/Al = 25) as catalyst. Moreover, the HZSM-5 catalyst was recycled for five times without significant decrease in product selectivity.
研究领域:
能源与燃料
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Catalysts
·
2025
·Vol. 15
·期 6
·530
·
IF 4
Yalin Guo,Zhuang Ma,Binbin Jin,Limin Ma,Guodong Yao
The sustainable valorization of lignocellulosic biomass into high-value platform chemicals presents a crucial pathway for reducing reliance on fossil resources. Gamma (γ)-valerolactone (GVL) has gained recognition as a versatile bio-derived compound with broad applications in renewable energy systems and green chemical synthesis. While conventional GVL production strategies from carbohydrate biomass typically depend on noble metal catalysts paired with high-pressure hydrogen gas, these approaches face substantial technical barriers including catalyst costs, hydrogen storage requirements, and operational safety concerns in large-scale applications. This work develops an innovative catalytic system utilizing earth-abundant iron for in situ hydrogen generation through water splitting, integrated with Raney Ni as the hydrogenation catalyst. The designed two-stage process enables direct conversion of cellulose—first through acid hydrolysis to levulinic acid (LA) followed by catalytic hydrogenation to GVL without intermediate purification. Through systematic parameter optimization, a remarkable 61.9% overall GVL yield from cellulose feedstock was achieved. Furthermore, the methodology’s versatility was demonstrated through wheat straw conversion experiments, yielding 24.6% GVL. This integrated methodology explores a technically feasible pathway for direct cellulose-to-GVL conversion utilizing abundant water as the hydrogen source, effectively overcoming the critical limitations associated with conventional hydrogenation technologies regarding hydrogen infrastructure and process safety.
研究领域:
生物化学
·
可再生能源
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Xinyu Wang,Mingyang Hu,Yun Liu
This study investigates a one-step process for the simultaneous separation of cellulose, hemicellulose, and lignin from lignocellulosic biomass using γ-valerolactone (GVL)/H 2 O pretreatment, which also converts hemicellulose to furfural (FF). A response surface methodology (RSM) was applied to optimize the process parameters. Under optimal conditions (163 °C for 1.5 h), the maximum FF yield reached 85.36 %, and cellulose purity was 80.80 %. The extracted GVL-lignin was characterized as low-molecular-weight guaiacyl-syringyl (G-S) type nanospheres with significant antioxidant activity. The conversion of hemicellulose to FF was enhanced by the synergistic interaction of Lewis acid (MgCl 2 ) and Brønsted acid (H 2 SO 4 ), which promoted the isomerization of xylose and dehydration to FF. The high-purity cellulose yielded 18.87 g/L ethanol through separate hydrolysis and fermentation (SHF), 27 times higher than untreated solids. Additionally, GVL exhibited consistent performance in lignocellulose separation after six cycles. This method offers an efficient and sustainable approach to valorize lignocellulosic biomass, advancing the production of high-value products.
研究领域:
生物化学
·
可再生资源与环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2019
·
IF 4.191
Xiaoyun Li,Jiaxin Yang,Rui Xu,Lefu Lu,Fangong Kong,Min Liang,Lijie Jiang,Shuangxi Nie,Chuanling Si
The production of platform chemicals from lignocellulosic biomass is scientifically valuable but technologically challenging. With the aim to establish a green reaction system for the production of furfural from lignocellulosic biomass, in the current work, H-SAPO-34 was investigated for catalysis of the conversion of Eucalyptus sawdust to furfural in γ-valerolactone (GVL). H-SAPO-34 was prepared and characterized by XRD, SEM, FTIR, BET, TGA and ammonia adsorbed FTIR. H-SAPO-34 possesses Brønsted and Lewis acid sites and a large specific surface area. The average pore diameter of H-SAPO-34 was 0.86 nm, which is beneficial for the spread of xylose and furfural and the inhibition of humin production. In this work, a peak furfural yield of 99.28% from Eucalyptus was achieved at 210 °C in 120 min with 30 g/L H-SAPO-34. The Brønsted/Lewis acid bifunctionality and the solvent effect of γ-valerolactone possibly contributed to the high furfural yield from real biomass. The kinetics of the conversion of Eucalyptus sawdust to furfural was also studied, and the activation energy for furfural production was calculated. Additionally, the catalytic activity and stability of the regenerated catalyst were estimated.
研究领域:
化学工程
·
可再生资源与环境科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）