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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2026 · IF 9.6

Controlled framework nickel exsolution in metal–organic frameworks creates confined active sites for chemoselective citral hydrogenation

Yifan Zhang,Tao Ban,Shihao Feng,Min Wang,Han Meng,Juan Chen,Hongyi Gao,Zhimeng Liu,Siqi Liu,Shuanglong Li,Ge Wang

Selective hydrogenation of citral to citronellal over non-noble-metal catalysts remains challenging because highly active metallic Ni simultaneously promotes efficient substrate activation and undesired over‑hydrogenation of the desired product. Herein, we develop a controlled exsolution strategy in waste polyethylene terephthalate (PET)-derived nickel metal–organic frameworks (Ni-MOFs) to transform framework Ni into confined metallic active sites while preserving the porous framework architecture. During reductive treatment, framework Ni 2+ species undergo gradual node-to-metal evolution, generating highly dispersed Ni 0 sites confined within the partially retained MOF framework. More importantly, the degree of framework Ni exsolution governs the balance between citral activation and citronellal over‑hydrogenation, thereby establishing a distinct chemoselective window. Within the optimal exsolution regime, the framework-confined Ni 0 sites enable efficient H 2 activation and selective hydrogenation of the C C bond while suppressing the subsequent hydrogenation of citronellal. Consequently, the optimized catalyst achieves ∼99% citral conversion and 100% citronellal selectivity at 90 °C and 2 MPa H 2 , together with excellent catalytic stability and recyclability. Beyond the sustainable valorization of waste PET, this work establishes controlled framework exsolution as an effective strategy for engineering confined active sites and regulating chemoselectivity in non-noble-metal hydrogenation catalysts. Figure. Controlled reduction of PET-derived Ni-BDC generates framework-confined Ni 0 species within the partially retained MOF structure, enabling selective hydrogenation of citral to citronellal. Download: Download high-res image (139KB) Download: Download full-size image

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JOURNAL OF APPLIED POLYMER SCIENCE · 2025 · IF 2.8

Chitosan–Citral Imine Hydrogels With Self-Ordered Nanostructures as Sustained-Release and Eco-Friendly Agricultural Fungicide

Linfeng Hu,Yunlong Wang,Hongying Niu,Hongxia Zhu

This study developed chitosan-based hydrogels as field-deployable carriers for sustained fungicide delivery to enhance crop disease resistance and yield. Citral and chitosan were reacted at three molar ratios (N1, N1.5, N2) via acid-catalyzed Schiff-base condensation, and the resulting hydrogels were characterized by FTIR, 1 H NMR, SEM and WXRD. Structural analyses confirmed the formation of self-ordered imine clusters with a d -spacing of 20.5 Å stabilized by non-covalent interactions. N1, the highest-cross-linked hydrogel, showed the best thermal stability ( T 10 = 160°C) and the lowest swelling, releasing 7.0% slower than N1.5 and 37.9% slower than N2. Antifungal assays demonstrated that N1 provided the strongest inhibition against five phytopathogens ( Rhizoctonia solani , Fusarium graminearum , Botrytis cinerea , Rhizoctonia cerealis , and Phytophthora capsici ), improving inhibition of B. cinerea , P. capsici , and F. graminearum by 56.8%, 82.9%, and 181.3%, respectively, compared with free citral. These hydrogels combine antifungal activity, water retention, thermal stability and controlled release, providing a promising strategy for green fungicide delivery in agriculture.

研究领域: 农业化学 · 高分子科学 · 植物病理学 · 绿色化学 · 药物递送系统
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MOLECULAR PLANT PATHOLOGY · 2023 · IF 4.9

Plant secondary metabolite citral interferes with Phytophthora capsici virulence by manipulating the expression of effector genes

Wen Song,Zhiyuan Yin,Xinyu Lu,Danyu Shen,Daolong Dou

Phytophthora capsici is a notorious pathogen that infects various economically important plants and causes serious threats to agriculture worldwide. Plants deploy a variety of plant secondary metabolites to fend off pathogen attacks, but the molecular mechanisms are largely unknown. In this study, we screened 11 plant secondary metabolites to evaluate their biofumigation effects against P. capsici , and found that citral, carvacrol, and trans -2-decenal exhibited strong antimicrobial effects. Intriguingly, a low concentration of citral was effective in restricting P. capsici infection in Nicotiana benthamiana , but it was unable to inhibit the mycelial growth. A high concentration of citral affected the mycelial growth and morphology, zoospore germination, and cell membrane permeability of P. capsici. Further investigations showed that citral did not induce expression of tested plant immunity-related genes and reactive oxygen species (ROS) production, suggesting that a low concentration of citral could not trigger plant immunity. Moreover, RNA-Seq analysis showed that citral treatment regulated the expression of some P. capsici effector genes such as RxLR genes and P. cactorum - fragaria (PCF)/small cysteine-rich (SCR)74-like genes during the infection process, which was also verified by reverse transcription-quantitative PCR assay. Five candidate effector genes suppressed by citral significantly facilitated P. capsici infection in N. benthamiana or inhibited ROS triggered by flg22, suggesting that they were virulence factors of P. capsici . Together, our results revealed that plant-derived citral exhibited excellent inhibitory efficacy against P. capsici by suppressing vegetative growth and manipulating expression of effector genes, which provides a promising application of citral for controlling Phytophthora blight.

CAS / MDL: 5392-40-5 499-75-2
研究领域: 植物病理学 · 分子生物学
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PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY · 2026 · IF 4.8

Synergistic antifungal activity of citral combined with its acylthiourea derivative against Rhizoctonia solani and its underlying mechanisms

Xiaoyi Pan,Hongyan Si,Suhua Yuan,Ruyin Li,Guoxiang Liao,Wuxiong Wang,Ji Zhang,Jie Song,Shangxing Chen,Shengliang Liao,Zongde Wang

Rhizoctonia solani is a significant soil-borne plant pathogenic fungus. Its sclerotial structure confers strong environmental adaptability and persistent infectivity, posing a serious threat to the production of numerous crops. Citral, a plant-derived monoterpene aldehyde, exhibits antifungal activity; however, its antifungal potency is limited. In this study, citral was combined with its acylthiourea derivatives, leading to the screening and construction of an efficient synergistic antifungal system, CE4. CE4 significantly inhibits mycelial growth of R. solani and reduces its capacity for sclerotia formation, with an EC 50 value of 10.97 mg/L. Further research has revealed that CE4 disrupts the surface structure of hyphae, significantly increases cell membrane permeability, and reduces ergosterol content, thereby disrupting cellular membrane homeostasis. Meanwhile, CE4 induces the accumulation of ROS and lipid peroxidation products, significantly disrupts the antioxidant enzyme system, and inhibits the activity of key enzymes in energy metabolism, thereby reducing ATP levels. Cytotoxicity evaluation demonstrated that CE4 did not significantly increase cytotoxicity toward mammalian cells at the effective antifungal concentration. The above results indicate that CE4 effectively inhibits the growth of R. solani through the synergistic disruption of cell membrane homeostasis, induction of oxidative stress, and interference with energy metabolism. The results of this study provide a novel theoretical and experimental foundation for the synergistic application of plant-derived antifungal agents.

CAS / MDL: 5392-40-5
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FOOD CHEMISTRY · 2022 · IF 9.231

Emulsification-based interfacial synthesis of citral-loaded hollow MIL-88A for the inhibition of potato tuber sprouting

Hao Huang,Fatima-ezzahra Ettoumi,Li Li,Yanqun Xu,Zisheng Luo

Economic value of the global potato harvest is impacted by sprouting during storage. We examined how sprouting might be reduced or eliminated using citral , a naturally occurring component in citrus fruit peel. The current study integrated both loading and sustained release of citral using emulsification-based interfacial synthesis of hollow MIL-88A. The structural properties and compositions of MIL-88A and hollow MIL-88A were confirmed using SEM, EDS, and XRD. BET analysis showed a surface area of 30.36 m 2 g −1 , pore volume of 0.21 cm 3 g −1 , and an average pore radius of 13.56 nm for hollow MIL-88A. Citral was successfully loaded into 10 g of MIL-88A and hollow MIL-88A, with a total citral load of 0.21 cm 3 and 1.82 cm 3 , respectively. The citral-loaded hollow MIL-88A induced a sustained release of citral, which effectively inhibited the sprouting, leading to higher starch content by 41%, lower weight losses, reducing sugar content, α-Amylase, β-amylase, and starch phosphorylase activities by 75%, 55%, 34%, 31%, and 43%, respectively. The citral-loaded hollow MIL-88A might inhibit sprouting by suppressing gibberellin and indole-3-acetic acid while maintaining abscisic acid.

研究领域: 农业科学 · 食品科学 · 材料科学 · 植物生理学
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Food Biophysics · 2026 ·Vol. 21 ·期 3 ·104 · IF 3.9

Preparation of Hydroxypropyl Methylcellulose-Fucoidan-Citral Nanoemulsion Composite Film: Characterization and Preservative Application in Ostrea rivularis Gould

Hu Yaqin,Liu Guangyu,Wang Dongxue,Yuan Chunhong,Wu Tiantian,Huang Jiayin,Xue Changfeng,Hu Zhiheng

Ostrea rivularis Gould ( O. rivularis ) is nutritionally rich oyster species highly perishable due to endogenous enzymatic activity and microbial proliferation. Currently, active packaging incorporating natural antimicrobials offers a promising approach to improve the quality and shelf-life of aquatic products. In this study, an active composite film (HPMC-FCD-CNE) was developed by incorporating citral nanoemulsion (CNE) into a hydroxypropyl methylcellulose (HPMC) and fucoidan (FCD) matrix. The film with 4% (v/v) CNE exhibited optimal mechanical and barrier properties alongside enhanced antioxidant and antibacterial activities. During refrigerated storage at 4 °C, oysters wrapped with the HPMC-FCD-CNE demonstrated a 4-day extension in shelf-life compared to unwrapped controls, with superior sensory acceptability and delayed quality deterioration, as indicated by reduced total volatile basic nitrogen (TVB-N), K value, and microbial counts. These findings highlight the potential of HPMC-FCD-CNE as an effective active packaging strategy to preserve oysters and other aquatic products under refrigeration.

CAS / MDL: 9004-65-3
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APPLIED BIOCHEMISTRY AND MICROBIOLOGY · 2025 · IF 1.1

Asymmetric Reduction of (E/Z)-citral to (R)-Citronellal by a Cyanobacterial-Derived Old Yellow Enzyme, CtOYE

Wu S. J.,Chen F.,Ma X. J.,Sun S. Y.,Yan H. D.,Li T. T.,Qiu L. Q.

( R )-citronellal is a key intermediate in the synthesis of L-menthol, one of the world’s three most important spices. It can be obtained by asymmetric reduction of ( E / Z )-citral using old yellow enzymes (OYEs), but catalysis by the wild-type enzyme suffers from poor enantioselectivity as well as low efficient conversion. A protein-directed evolution technique was used to enhance the activity and enantioselectivity of Ct OYE from Chroococcidiopsis thermalis . Upon the sequence alignment and molecular docking results, two amino acid residues at positions 103 and 351 were selected as saturation mutation sites. Finally, three single substitution variants of Ct OYE-W103E, Ct OYE-W103M, Ct OYE-W103P with improved enantioselectivity ( ee > 99%) and moderate conversion (>71%), and one double substitution variant Ct OYE-Y351Q/W103E with high enantioselectivity ( ee > 99%) and high conversion (83.2%) for reduction of ( E / Z )-citral were obtained.

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Carbohydrate Polymer Technologies and Applications · 2025 · IF 6.5

Preparation and characterization of carboxymethyl cellulose-based edible thin films loaded with rosmarinic acid and citral nanoparticles

Jinhua Zhang,Jichen Su,Xinyi Liu,Min Chen,Baoqing Bai,Yukun Yang,Sanhong Fan,Tao Bo

s This study aimed to prepare a CS-TPP nanoparticle loaded with rosmarinic acid and citral and to evaluate the overall performance of the novel antimicrobial film prepared by the addition of the nanoparticles to the CMC film. The structure of the nanoparticles was determined by particle size potentiometry, SEM, and FTIR, and it was demonstrated that rosemarinic acid and citral were successfully combined with CS-TPP nanoparticles with a particle size of 446.2 nm. The surface morphology and mechanical properties of the films were determined by texture instrumentation, SEM, FTIR, and XRD.The CMC-XT showed a tensile strength of 9.30 N/mm² (49 % higher than the blank film, 6.23 N/mm²) and an elongation at break of 175 %, surpassing the CMC-RA (6.58 N/mm²). The antibacterial performance experiment showed that the inhibition rates of CMC-XT on E.coli and S.aureus were 69.4 % and 61.9 %, respectively, which were significantly better than the blank membrane (9.2 %).The experiment provides a new type of film that combines mechanical strength, antibacterial performance, and environmental friendliness for food preservation, solving the safety issues of traditional chemical preservatives and the cost limitations of physical preservation technology.As well as it utilizes natural antimicrobial agents and biodegradable polymers, reducing reliance on traditional chemical preservatives that may pose health risks or environmental concerns.

CAS / MDL: 7758-29-4
研究领域: 食品科学 · 材料科学
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FOOD SCIENCE AND BIOTECHNOLOGY · 2025 · IF 3.1

Synergistic combination of cinnamaldehyde with citral for improving bread preservation: inhibition of Aspergillus niger and Penicillium citrinum

Tan Jin-Ming,Cui Rui,Hu Teng-Gen,Wu Hong

In order to improve the antifungal activity of natural fungicides to control the fungal contamination on bread products, the synergistic combination of cinnamaldehyde with citral (S CC ) against main bread spoilage fungi ( Aspergillus niger and Penicillium citrinum ) was screened. Compared to the single MICs of cinnamaldehyde and citral, the MICs of them against both fungi were significantly reduced by 74–87% when presented in S CC . In vitro tests demonstrated that S CC completely inhibited the spore germination and mycelial growth of both fungi at its MIC. Mechanistic investigations revealed that S CC caused severe cellular membrane damage and disrupted the intracellular redox homeostasis in both fungi. In situ tests showed S CC significantly extended the shelf life of bread by 9 days without adversely affecting the sensory flavor and quality of the bread. These results indicated that S CC is potential as a natural preservative in baked products.

研究领域: 食品科学 · 微生物学
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Bioresources and Bioprocessing · 2018 ·Vol. 5 ·期 1 ·1-12 · IF 0

Identification of a yeast old yellow enzyme for highly enantioselective reduction of citral isomers to (R)-citronellal

Zheng Liandan,Lin Jinping,Zhang Baoqi,Kuang Yuyao,Wei Dongzhi

A NAD(P)H-dependent enoate reductase (OYE2p) from Saccharomyces cerevisiae YJM1341 was discovered by genome data mining for asymmetric reduction of (E/Z)-citral to (R)-citronellal with high enantioselectivity.This enzyme was heterologously expressed in E. coli and characterized for its biocatalytic properties. OYE2p was identified with reduction activities toward a diverse range of ɑ,β-unsaturated compounds bearing conjugated aldehyde, ketone, imide, carboxylic acid and ester.OYE2p showed the highest specific activity at 40 °C and a pH optimum at 7.0–8.0. The stability of OYE2p was rather pH-independent, and the half-life time values of the enzyme at pH 6.0–8.0 were more than 257 h. With regard to the reduction of (E)-citral and (Z)-citral, OYE2p exhibited different selectivity patterns. (E)-citral was exclusively reduced to (R)-citronellal by OYE2p in ≥ 99% ee, which was independent on pH. OYE2p produced both enantiomers of citronellal from (Z)-citral, but showed (R)-citronellal formation tendency, and the ee value of (R)-citronellal was affected by pH in the reaction system. Accordingly, the ee values for (R)-citronellal formation increased with the increasing levels of E-isomer in the (E/Z)-citral mixture as well as the increase of pH. Under the reaction conditions (30 °C and pH 8.6), using purified OYE2p as catalyst, 200 mM (E/Z)-citral (an approximately 10:9 mixture of geometric E-isomer and Z-isomer) was efficiently converted to (R)-citronellal with 88.8% ee and 87.2% yield.All these positive features demonstrate high potential of OYE2p for practical synthesis of (R)-citronellal and in asymmetric reduction of activated alkenes.

研究领域: 生物化学 · 酶工程 · 合成生物学
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Journal of Fungi · 2022 ·Vol. 8 ·期 4 ·388 · IF 5.724

Antifungal Activity of Polymethoxylated Flavonoids (PMFs)-Loaded Citral Nanoemulsion against Penicillium italicum by Causing Cell Membrane Damage

Long Guo,Yi Li,Xiaoxue Mao,Rui Tao,Boyun Tao,Zhiqin Zhou

A major citrus postharvest pathogen,Penicilliumitalicum(P. italicum), causes substantial economic losses in citrus. In this study, a citral nanoemulsion containing polymethoxylated flavonoids (PMFs), the antimicrobial compounds from citrus, was prepared. The antifungal activity and potential antifungal mechanisms of the nanoemulsion againstP. italicumwere evaluated. The results showed that the growth ofP. italicumwas effectively inhibited by the nanoemulsion, with a minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) of 62.5 and 250 mg L−1, respectively. The nanoemulsion significantly inhibited spore germination and mycelial growth, and it altered the morphology ofP. italicum. In addition, the permeability of the cell membrane increased with increasing nanoemulsion concentrations, as evidenced by a rapid rise in extracellular electric conductivity and stronger red fluorescence from mycelia (propidium iodide staining). Compared with the control, the nanoemulsion treatment induced a decrease in total lipid and ergosterol contents inP. italicumcells by 64.61% and 60.58%, respectively, demonstrating that membrane integrity had been disrupted. The results indicated that the PMFs-loaded nanoemulsion exerted antifungal activity againstP. italicumby disrupting cell membrane integrity and permeability; such a nanoemulsion may be used as a potential fungicide substitute for preservation in citrus fruits.Keywords:antifungal mechanism;citrus blue mold;membrane integrity;membrane permeability;P. italicum

CAS / MDL: 5392-40-5
研究领域: 植物病理学 · 食品科学 · 药理学
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Molecular Catalysis · 2021 · IF 5.062

Mesoporous tin phosphate as an effective catalyst for fast cyclodehydration of bio-based citral into p-cymene

Jian He,Zhaozhuo Yu,Hongguo Wu,Hu Li,Song Yang

Effective synthesis of aromatic compounds from renewable biomass is highly important yet challenging. p -Cymene is an attractive aromatic compound with various promising applications in the manufacture of fine chemicals. In this study, a novel and effective catalytic system based on mesoporous tin phosphate (M-SnPO) with Lewis-Brønsted dual acidity was developed for the fast synthesis of p -cymene from the cyclodehydration of bio-based citral. Up to 78.5% yield of p -cymene was achieved from the cyclodehydration of citral at 180 °C within only 0.5 h, superior to the results reported for benchmark homogeneous acid catalysts. Characterization of as-prepared M-SnPO catalyst via various techniques indicates that the synergic effect of Lewis and Brønsted acidic sites, large pore-sized structure, and high surface area are responsible for its remarkable catalytic performance. In addition, the effectiveness of the M-SnPO catalyst could be almost sustained over multiple cycles without significant loss. The work herein is the first example of developing a Lewis-Brønsted dual acidic heterogeneous catalyst for the fast synthesis of p -cymene from the cyclodehydration of citral.

研究领域: 催化化学 · 生物质转化 · 材料科学
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