JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
·
2025
·
IF 6.2
Yu Du,Xiang Lv,Till Siebenmorgen,Grzegorz Popowicz,Chenhao Feng,Yunjian Ma,Yonghua Wang
Enzymatic synthesis of δ-lactones using Baeyer–Villiger monooxygenases (BVMOs) has potential in the fragrance and flavor industries but is constrained by poor activity toward ortho-alkyl-substituted cyclopentanones, key δ-lactone precursors. We determined the crystal structure of a BVMO derived from Oceanicola granulosus (OgBVMO), uncovering a unique loop adjacent to key catalytic residue R335. Site-saturation mutagenesis of loop residues A338 and A339 identified the A339E variant, obtaining a 2.4- to 3-fold increase in catalytic activity toward ortho-alkyl-substituted cyclopentanones (2-methyl-, 2-ethyl-, 2-hexyl-, and 2-heptylcyclopentanone). Further engineering the substrate-binding pocket yielded the Q442N variant, improving activity by 2.7–3.8-fold. Remarkably, the combinatorial mutant A339E/Q442N achieved 3.3–5.2-fold higher activity than the wild-type. Molecular dynamics simulations indicated that these improvements were driven by more favorable nucleophilic attack distances, underscoring the synergistic effects of distal and active-site mutations. These findings offer valuable insights into enhancing the catalytic activity of BVMOs, supporting the green manufacturing of high-value flavor compounds.
研究领域:
生物化学
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合成生物学
·
酶学
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Pengyu Yuan,Qing Wang,Xuelei Deng,Xiaoyan Zhang,Daidi Fan,Yunpeng Bai
Enzyme catalysis is a promising method for producing chiral chemicals with high stereoselectivity under mild conditions. However, the traditional batch reaction suffers from low enzyme stability, low cofactor recycling, and poor enzyme reusability. Here, we present a continuous-flow method using coimmobilized dual enzymes for the synthesis of chiral γ-/δ-lactones, which are widely used in fragrances and flavors. Typically, a carbonyl reductase mutant SmCRM5 from Serratia marcescens, was coimmobilized by covalent binding with BmGDH, a glucose dehydrogenase capable of recovering and recycling the cofactor NADPH. After immobilization, SmCRM5 and BmGDH exhibited a 8.9-/8.7-fold increase in catalytic efficiency (kcat/Km) and a 57-/15-fold increase in half-life at 30 °C, respectively. We demonstrated that coimmobilized dual enzymes used in a continuous flow reactor showed a higher reaction rate and a higher space-time yield (1586 g·L–1 d–1) than free enzymes and immobilized enzymes in a batch reaction for the production of (R)-δ-decalactone. This continuous flow reactor can run continuously for more than 650 h with 99% ee and 80% conversion, and the total volume exceeds 1500 reactor volumes. The robustness of this continuous-flow immobilized enzyme system provides a green and efficient method for the synthesis of high value-added chiral chemicals.
研究领域:
生物催化
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酶工程
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绿色化学
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DOI
PubMed
高影响因子
ChemCatChem
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2019
·Vol. 11
·期 11
·2600-2606
·
IF 4.495
Meng Chen,Xiao-Yan Zhang,Chen-Guang Xing,Chao Zhang,Yu-Cong Zheng,Jiang Pan,Jian-He Xu,Yun-Peng Bai
Graphical Great engineering ! In this work, structurally diverse γ- and δ-lactones were efficiently stereoselectively synthesized using an engineered carbonyl reductase from Serratia marcescens ( Sm CR V4 ). Sm CR V4 exhibited improved activity and thermostability toward 14 γ-/δ-keto acids and esters compared with the wild-type enzyme, with 110-fold enhancement in catalytic efficiency ( k cat / K m ) toward methyl 4-oxodecanoate. The preparative synthesis of alkyl and aromatic γ- and δ-lactones with 95 %–>99 % ee was demonstrated. The highest space-time yield, 1175 g L −1 d −1 , was achieved for ( R )-γ-decalactone. Structurally diverse γ- and δ-lactones were efficiently synthesized stereoselectively using an engineered carbonyl reductase from Serratia marcescens ( Sm CR V4 ). Sm CR V4 exhibited improved activity (up to 500-fold) and thermostability toward 14 γ-/δ-keto acids and esters, compared with the wild-type enzyme, with 110-fold enhancement in catalytic efficiency ( k cat / K m ) toward methyl 4-oxodecanoate. The preparative synthesis of alkyl and aromatic γ- and δ-lactones with 95 %–>99 % ee and 78 %–90 % yields was demonstrated. The highest space-time yield, 1175 g L −1 d −1 , was achieved for ( R )-γ-decalactone.
研究领域:
生物化学
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酶工程
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有机合成
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DOI
高影响因子
INTERNATIONAL JOURNAL OF PHARMACEUTICS
·
2017
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IF 3.649
Xin Xu,Yan Li,Liping Liu,Yuhong Li,Guomei Ru,Qiannan Ding,Liping Deng,Jian Dong
Novel biocompatible and biodegradable polymers are highly desirable and crucial in drug delivery applications in order to overcome the technical challenges and problems existing in the traditional method of poly(ethylene glycol) based drug carriers. In this study, ring-opening polymerization of a carbohydrate-derived lactone , glucono-δ-lactone (GDL), generates a new highly branched polymer (PGDL) that can form stable nanoparticles through a w/o emulsification approach. The biodegradable and biocompatible particles can carry anticancer agent 5-fluorouracil (5-FU) effectively. The controlled release of 5-FU from the PGDL particles exhibits a non-Fickian mechanism without an initial burst, with an enhanced release exponent at tumoral pH. Cell viability studies by MTT assays indicate that ovarian carcinoma cells (OVCAR-3) and macrophage cells (raw 264.7) treated with PGDL (2.5 mg/ml) show no signs of toxicity in 24 h cell incubations. The PGDL particles can interact with the OVCAR-3 cell line efficiently. Therefore, the glucono-δ-lactone based particles represent an effective delivery system for cancer therapy.
研究领域:
生物医学工程
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药剂学
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肿瘤学
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DOI
PubMed
高影响因子
JOURNAL OF ORGANOMETALLIC CHEMISTRY
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2011
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IF 2.205
Yao Dai,Xiujuan Feng,Bin Wang,Ren He,Ming Bao
Air-stable P , N -bidentate ligands L1 – L7 with cyclic secondary amine moieties linked to the benzene rings of triphenylphosphine were designed and prepared. The chelating coordination mode of the P , N -bidentate ligands to the Pd(II) center was confirmed by determining the X-ray structures of the Pd(II) complexes C1 and C2 derived from ligands L1 and L2 , respectively. The ligands were used for the selective synthesis of δ -lactone through the palladium (Pd)-catalyzed telomerization of 1,3-butadiene with carbon dioxide. The highest yield (60% with 79% selectivity) was observed using the Pd 2 (dba) 3 /4-(2-(diphenylphosphino)phenyl)morpholine ( L2 ) catalyst system.
研究领域:
有机化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Liang Zhou,Zhen Liu,Guanglong Dai,Ruxiang Qin
To address the environmentally friendly issue of fire prevention and extinguishing materials in coal mines, a new type of mine fire prevention and extinguishing gel was prepared using sodium carboxymethyl cellulose (CMC) as the matrix, ferro aluminum citrate (Fe-AlCit) as the cross-linking agent, and gluconic acid-δ-lactone (GDL) as the pH modifier. The preferred ratio was 2.5 % CMC + 4 % Fe-AlCit + 2 % GDL of No. 23 gel material by gelation time, thermal stability, strength, and permeability performance tests. The results show that the gelation time of No. 23 gel was 10 min, and its complete water loss time was 1.97 times that of water at a high temperature of 180 °C. The gel for sealing the surface of the coal body still maintained good stability after two weeks. Furthermore, A metal coordination bond favorable to the stability of gel is formed by the carboxylate ion in CMC and the double high-valent metal ions Fe 3+ and Al 3+ ionized by Fe-AlCit. No. 23 gel exhibits excellent fire prevention and extinguishing properties. The temperature-programmed test showed that the CO and C 2 H 4 gas inhibition rate of the coal sample treated with No. 23 gel reached 33.42 % and 56.86 % at 220 ℃, and the activation energy growth rate reached 26.5 % and 21.1 % in the first and second stages, respectively. The fire extinguishing test indicated that No. 23 gel can significantly reduce the temperature of the coal sample and extinguish the coal fire quickly. The study is useful to develop efficient and environmentally friendly coal mine fire prevention and extinguishing materials.
研究领域:
矿业工程
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环境科学
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产品关联
DOI
高影响因子
FOOD RESEARCH INTERNATIONAL
·
2024
·
IF 7
Yanfei Xu,Zheng Zhou
While heat treatment is a conventional method for the gelation of alkaline-extracted walnut protein isolates (AWPI), it can limit the incorporation of heat-sensitive ingredients. This study explored a novel approach to fabricate cold-set gels from epigallocatechin-3-gallate (EGCG) conjugated AWPI (AWPI-EGCG). EGCG conjugation effectively inhibited the thermal gelation of AWPI while promoting the formation of soluble aggregates upon heat treatment. AWPI-EGCG cold-set gels were then successfully fabricated through acidification with glucono-δ-lactone (GDL). The rheological study revealed that the storage modulus and yield stress of the cold-set gels were positively correlated with the GDL concentration and the EGCG conjugation degree. However, higher concentrations of GDL were associated with the reduced yield strain of the gels. Texture analysis indicated an increase in gel hardness with increasing GDL concentration, accompanied by a decrease in springiness. Microstructural examination by scanning electron microscopy revealed that the AWPI-EGCG cold-set gels with 0.3 % GDL exhibited smaller pores with thinner and smoother internal walls, while those with 0.9 % GDL exhibited relatively larger pores with thicker and denser walls. In addition, the AWPI-EGCG cold-set gels showed promising quercetin encapsulation capacities and controlled release properties.
研究领域:
食品科学
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生物技术
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FOOD HYDROCOLLOIDS
·
2024
·
IF 11
Qi Qi,Xiaopian Yan,Yuxuan Mao,Fang Wang,Hao Zhang,Xiuying Xu,Yuzhu Wu,Chengbin Zhao,Jingsheng Liu
Soybean protein isolate (SPI) and red bean protein isolate (RBPI) were mixed with common starch (CS) and waxy starch (WS) from corn respectively, and then subjected to glucono-δ-lactone (GDL)-induced crosslinking to form the protein–starch complex cold gels, which was used as a delivery carrier for curcumin. The complex gel with addition of CS had denser network structure and higher gel strength, resistance to deformation and viscoelasticity, while the complex gel with WS had the opposite effect. The protein interacted more strongly with CS than WS, enhancing the structural and thermal stability of the complex gel, which resulted in a higher curcumin encapsulation ratio in the gel and its chemical stability during light and heat treatment. The intensity and location of many characteristic absorption peaks in the infrared spectra changed during simulated gastrointestinal digestion, which indicated the destruction of gel structure, leading to the transformation of α-helix and β-sheet into β-turn and random coil in the secondary structure. The addition of CS and WS reduced the release of curcumin in gastric phase, but promoted its directional release in intestinal phase, due to the changes in the digestion pattern of the complex gel, especially the complex gel with addition of WS had a better controlled release effect, which was also related to the more disordered and flexible secondary structure of its gastric digests. The protection of curcumin by gel network and the targeted release behavior of curcumin during intestinal digestion improved its bioaccessibility. In addition, the curcumin in RBPI-based gels had higher encapsulation ratio, chemical stability and bioaccessibility than that in SPI-based gels. Therefore, protein–starch complex cold gels can be used as controlled release carriers for the protection and delivery of sensitive bioactive compounds or nutrients.
研究领域:
食品科学
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生物技术
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药学
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材料科学
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产品关联
DOI
高影响因子
FOOD HYDROCOLLOIDS
·
2018
·
IF 5.089
Wei Liu,Hongxia Gao,David Julian McClements,Lei Zhou,Jing Wu,Liqiang Zou
High internal phase emulsions (HIPEs) were prepared using preheated whey protein isolate (WPI). The influence of cold-set gelation induced by addition of glucono-δ-lactone (GDL) on the microstructure, rheology, water holding capacity (WHC), and stability of HIPEs was determined. In the presence and absence of GDL, the mean particle diameters of HIPEs decreased with increasing WPI concentration. The addition of GDL to the HIPEs did not alter their mean particle diameter or microstructure. The gel strength, hardness, WHC, and stability of HIPEs increased with increasing WPI concentration and with GDL addition. An in vitro digestion experiment showed that β-carotene retention and bioaccessibility was higher after GDL was added to the HIPEs. These findings may be useful for the development of HIPE-based delivery systems for food and other applications.
研究领域:
食品科学
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化学工程
·
营养学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Shuo Wang,Guochao Xu,Ye Ni
A novel carbonyl reductase from Hyphopichia burtoni ( Hb KR) was discovered by gene mining. Hb KR is a NADPH-dependent dual function enzyme with reduction and oxidation activity belonging to SDR superfamily. Hb KR strictly follows Prelog priority in the reduction of long-chain aliphatic keto acids/esters containing remote carbonyl groups, such as 4-oxodecanoic acid and 5-oxodecanoic acid, producing ( S )- γ -decalactone and ( S )- δ -decalactone in >99 % e.e. Tailor-made engineering of Hb KR was conducted to improve its catalytic efficiency . Variant F207A/F86M was obtained with specific activity of 8.37 U/mg toward 5-oxodecanoic acid, which was 9.7-fold of its parent. Employing F207A/F86M, 100 mM 5-oxodecanoic acid could be reduced into optically pure ( S )- δ -decalactone. Molecular docking analysis indicates that substitution of aromatic Phe with smaller residues renders sufficient space for accommodating substrates in a more stable conformation. This study offers an efficient biocatalyst for the biosynthesis of ( S )-lactones, and provides guidance for engineering carbonyl reductases toward structurally hindered substrates.
研究领域:
生物化学
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生物技术
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酶工程
·
有机化学
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产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-12
·
IF 14.7
Zhang Jinbo,Jiang Lihang,Liu Shaofeng,Shen Junhao,Braunstein Pierre,Shen Yong,Kang Xiaohui,Li Zhibo
When aiming at the direct use of CO 2 for the preparation of advanced/value-added materials, the synthesis of CO 2 /olefin copolymers is very appealing but challenging. The δ-lactone 3-ethylidene-6-vinyltetrahydro-2 H -pyran-2-one (EVP), synthesized by telomerization of CO 2 with 1,3-butadiene, is a promising monomer. However, its chemoselective ring-opening polymerization (ROP) is hampered by unfavorable thermodynamics and the competitive polymerization of highly reactive C=C double bonds under usual conditions. Herein, we report the chemoselective ROP of EVP using a phosphazene/urea binary catalyst, affording exclusively a linear unsaturated polyester poly(EVP) ROP , with a molar mass ( M n ) up to 16.1 kg·mol −1 and a narrow distribution ( Ð < 1.6), which can be fully recycled back to the pristine monomer, thus establishing a monomer-polymer-monomer closed-loop life cycle. In these polyesters, the CO 2 content reaches 33 mol% (29 wt%). The reasons for the unexpected chemoselectivity were investigated by Density-functional theory (DFT) calculations. The poly(EVP) ROP features two pendent C=C double bonds per repeating unit, which show distinct reactivity and thus can be properly engaged in sequential functionalizations towards the synthesis of bifunctional polyesters. We disclose here a methodology providing a facile access to bifunctional and recyclable polyesters from readily available feedstocks.
研究领域:
材料科学
·
高分子化学
·
可持续化学
·
催化
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产品关联
DOI
PubMed
高影响因子
Journal of the Mechanical Behavior of Biomedical Materials
·
2022
·
IF 4.042
Yexiao Guan,Yanrui Mao,Jianguo Liao
In this paper, given the lack of osteogenic activity of sodium alginate (SA) hydrogel and to simulate the composition of natural bone, ionic-crosslinking NBG/n-HA/SA hydrogel scaffolds were prepared by using nano bioactive glass (NBG) and nano hydroxyapatite (n-HA) with high bioactivity as composite calcium sources and reinforcement phases, and D-gluconic acid δ-lactone (GDL) as the coagulant. The results showed that the mixture of the precursor forming the network had good injectability and plasticity. When the dosage of GDL was 0.75 g, the gelling time of the composite hydrogel could be regulated within 4–8 min, and the hydrogel had high compressive strength (170–220 kPa), as well. When the mass ratio of calcium source to SA was 1:1, the crosslinking network was relatively uniform with a considerable number of large pores around 40 μm in the structure. In the immersion experiment in vitro, it was found that the composite hydrogel could promote the deposition of bone-like apatite on the material's surface. Meanwhile, the cell experiments in vitro verified that the NBG/n-HA/SA composite hydrogel had good cytocompatibility without cytotoxicity. Moreover, the composite hydrogel could enhance the activity of ALP of mouse bone marrow mesenchymal stem cells , and thus, it had good osteogenic activity.
研究领域:
生物材料
·
组织工程
·
生物医学工程
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）