Fatty acid profile, minor bioactive constituents and physicochemical properties of insect-based oils: A comprehensive review.

Insect-based food or ingredients have received tremendous attention worldwide because of their potential to ensure food and nutrition security, mitigating the reliance on land-dependent agricultural products. Indeed, insect-farming has low environmental impacts with reduced land, water and energy input. More importantly, insects are rich in high quality proteins and fats. They are also excellent sources of minerals, vitamins and bioactive compounds. Insect-based lipids are intriguing because they may contain high levels of unsaturated fatty acids particularly linoleic and α-linolenic acids. Besides, the insect-based lipids also show a considerable amount of bioactive components such as tocols, sterols and carotenoids. However, their fatty acid compositions and the nutritional values may vary depending on species, feed composition, developmental stage, geographical locations, and extraction techniques. Therefore, the present article aims to provide a comprehensive review on the fatty acid composition, the minor bioactive constituents and the physicochemical properties of fats and oils derived from insects of different orders (Coleoptera, Lepidoptera, Hymenoptera, Orthoptera, Hemiptera and Diptera). The various parameters affecting the nutritional compositions of the insect-based lipids will also be highlighted. These information will definitely provide a detailed insight on the potential applications of these fats in various food systems based on their unique properties.

Medium chain triglyceride and medium-and long chain triglyceride: metabolism, production, health impacts and its applications - a review.

Structured lipid is a type of modified form of lipid that is "fabricated" with the purpose to improve the nutritional and functional properties of conventional fats and oils derived from animal and plant sources. Such healthier choice of lipid received escalating attention from the public for its capability to manage the rising prevalence of metabolic syndrome. Of which, medium-chain triacylglycerol (MCT) and medium-and long-chain triacylglycerol (MLCT) are the few examples of the "new generation" custom-made healthful lipids which are mainly composed of medium chain fatty acid (MCFA). MCT is made up exclusively of MCFA whereas MLCT contains a mixture of MCFA and long chain fatty acid (LCFA), respectively. Attributed by the unique metabolism of MCFA which is rapidly metabolized by the body, MCFA and MCT showed to acquire multiple physiological and functional properties in managing and reversing certain health disorders. Several chemically or enzymatically oils and fats modification processes catalyzed by a biological or chemical catalyst such as acidolysis, interesterification and esterification are adopted to synthesis MCT and MLCT. With their purported health benefits, MCT and MLCT are widely being used as nutraceutical in food and pharmaceutical sectors. This article aims to provide a comprehensive review on MCT and MLCT, with an emphasis on the basic understanding of its structures, properties, unique metabolism; the current status of the touted health benefits; latest routes of production; its up-to-date applications in the different food systems; relevant patents filed and its drawbacks.

Pickering emulsion-templated ionotropic gelation of tocotrienol microcapsules: effects of alginate and chitosan concentrations and gelation process parameters.

BACKGROUND: Throughout the past decade, Pickering emulsion has been increasingly utilized for the encapsulation of bioactive compounds due to its high stability and biocompatibility. In the present work, palm tocotrienols were initially encapsulated in a calcium carbonate Pickering emulsion, which was then subjected to alginate gelation and subsequent chitosan coating. The effects of wall material (alginate and chitosan) concentrations, gelation pH and time, and chitosan coating time on the encapsulation efficiency of palm tocotrienols were explored. RESULTS: Our findings revealed that uncoated alginate microcapsules ruptured upon drying and exhibited low encapsulation efficiency (13.81 ± 2.76%). However, the addition of chitosan successfully provided a more complex and rigid external wall structure to enhance the stability of the microcapsules. By prolonging the crosslinking time from 5 to 30 min and increasing the chitosan concentration from 0.1% to 0.5%, the oil encapsulation efficiency was increased by 28%. Under the right gelation pH (pH 4), the extension of gelation time from 1 to 12 h resulted in an increase in alginate-Ca2+ crosslinkings, thus strengthening the microcapsules. CONCLUSION: With the optimum formulation and process parameters, a high encapsulation efficiency (81.49 ± 1.75%) with an elevated oil loading efficiency (63.58 ± 2.96%) were achieved. The final product is biocompatible and can potentially be used for the delivery of palm tocotrienols. © 2021 Society of Chemical Industry.

Production, safety, health effects and applications of diacylglycerol functional oil in food systems: a review.

Diacylglycerol (DAG) is a world leading anti-obesity functional cooking oil synthesized via structural modification of conventional fats and oils. DAG exits in three stereoisomers namely sn-1,2-DAG, sn-1,3-DAG, and sn-2,3-DAG. DAG particularly sn-1,3-DAG demonstrated to have the potential in suppressing body fat accumulation and lowering postprandial serum triacylglycerol, cholesterol and glucose level. DAG also showed to improve bone health. This is attributed to DAG structure itself that caused it to absorb and digest via different metabolic pathway than conventional fats and oils. With its purported health benefits, many studies attempt to enzymatically or chemically synthesis DAG through various routes. DAG has also received wide attention as low calorie fat substitute and has been incorporated into various food matrixes. Despite being claimed as healthy cooking oil the safety of DAG still remained uncertain. DAG was banned from sale as it was found to contain probable carcinogen glycidol fatty acid esters. The article aims to provide a comprehensive and latest review of DAG emphasizing on its structure and properties, safety and regulation, process developments, metabolism and beneficial health attributes as well as its applications in the food industry.

Interesterified palm olein lowers postprandial glucose-dependent insulinotropic polypeptide response in type 2 diabetes.

PURPOSE: We aim to investigate the postprandial effects of palm olein (PO) and chemically interesterified palm olein (IPO) with different proportions of palmitic acid at the sn-2 position using high oleic sunflower oil (HOS) as control fat on concentrations of gut hormones, glucose homeostasis, satiety, lipid and inflammatory parameters in type 2 diabetic (T2D) subjects. METHODS: Using a randomised double-blind crossover design, 21 (men = 6, women = 15) T2D subjects consumed test meals (3.65 MJ) consisting of a high fat muffin (containing 50 g test fats provided as PO, IPO or HOS) and a milkshake. Postprandial changes in gut hormones, glucose homeostasis, satiety, lipid and inflammatory parameters after meals were analysed. Some of the solid fractions of the IPO were removed and thus the fatty acid composition of the PO and IPO was not entirely equal (PO vs IPO: palmitate 39.8 vs 38.7; oleate 43.6 vs 45.1). PO, IPO and HOS contained 9.7, 38.9 and 0.2 g/100 g total fatty acids of palmitic acid at the sn-2 position, respectively. At 37 °C, IPO contained 4.2% SFC whereas PO and HOS were completely melted. RESULTS: Our novel observation shows that the incremental area under curve (iAUC) 0-6 h of plasma GIP concentration was on average 16% lower following IPO meal compared with PO and HOS (P < 0.05) meals. Serum C-peptide concentrations exhibited a significant meal × gender interaction (P = 0.009). No differences between test meals were noted for other measurements. CONCLUSIONS: This study shows no adverse effect of interesterification on hormones associated with glucose homeostasis notably GLP-1 in T2D subjects. TRIAL REGISTRATION: ClinicalTrials.gov NCT01906359. https://clinicaltrials.gov/ct2/show/NCT01906359.

Evaluation of quality parameters for fresh, used and recycled palm olein.

BACKGROUND: Recycled oil has emerged as a significant food safety issue and poses a major threat to public health. To date, very limited studies have been conducted aiming to detect the adulteration of used and recycled palm olein in refined, bleached and deodorized palm olein (RBDPO). In the present study, oil samples that underwent controlled heating and deep-frying studies were refined using the common oil refining procedure to simulate the production of recycled oil. Polymerized triacylglycerol (PTG), oxidized monomeric triacylglycerols (oxTAGs), such as epoxy, keto and hydroxy acids, and caprylic acid have been proposed as potential indicators for tracking the adulteration of recycled oil. RESULTS: For PTG, triacylglycerol oligomers and dimers showed a significant increase (P < 0.05) after the refining process. Although there was a significant reduction (P < 0.05) in the total oxTAGs concentration after refining, they were still present in the recycled palm olein, even though the used palm olein had undergone a complete oil refining process. The concentration of caprylic acid increased significantly (P < 0.05) in palm olein after undergoing various heat and deep-frying treatments and even showed a significant (P < 0.05) increase in recycled oil. CONCLUSION: The results obtained in the present study justify the suitability of the proposed quality parameters for use as quality indices with respect to controlling the adulteration of used and recycled palm olein in RBDPO for the protection of the health and safety of consumers. © 2019 Society of Chemical Industry.

New functionalities of Maillard reaction products as emulsifiers and encapsulating agents, and the processing parameters: a brief review.

Non-enzymatic browning has been a wide and interesting research area in the food industry, ranging from the complexity of the reaction to its applications in the food industry as well as its ever-debatable health effects. This review provides a new perspective to the Maillard reaction apart from its ubiquitous function in enhancing food flavour, taste and appearance. It focuses on the recent application of Maillard reaction products as an inexpensive and excellent source of emulsifiers as well as superior encapsulating matrices for the entrapment of bioactive compounds. Additionally, it will also discuss the latest approaches employed to perform the Maillard reaction as well as several important reaction parameters that need to be taken into consideration when conducting the Maillard reaction. © 2016 Society of Chemical Industry.

Palm-based medium-and-long-chain triacylglycerol (P-MLCT): production via enzymatic interesterification and optimization using response surface methodology (RSM).

Structured lipid such as medium-and long-chain triacylglycerol (MLCT) is claimed to be able to suppress body fat accumulation and be used to manage obesity. Response surface methodology (RSM) with four factors and three levels (+1,0,-1) faced centered composite design (FCCD) was employed for optimization of the enzymatic interesterification conditions of palm-based MLCT (P-MLCT) production. The effect of the four variables namely: substrate ratio palm kernel oil: palm oil, PKO:PO (40:60-100:0 w/w), temperature (50-70 °C), reaction time (0.5-7.5 h) and enzyme load (5-15 % w/w) on the P-MLCT yield (%) and by products (%) produced were investigated. The responses were determined via acylglycerol composition obtained from high performance liquid chromatography. Well-fitted models were successfully established for both responses: P-MLCT yield (R (2) = 0.9979) and by-products (R (2) = 0.9892). The P-MLCT yield was significantly (P < 0.05) affected by substrate ratio, reaction time and reaction temperature but not enzyme load (P > 0.05). Substrate ratio PKO: PO (100:0 w/w) gave the highest yield of P-MLCT (61 %). Nonetheless, substrate ratio of PKO: PO (90:10w/w) was chosen to improve the fatty acid composition of the P-MLCT. The optimized conditions for substrate ratio PKO: PO (90:10 w/w) was 7.26 h, 50 °C and 5 % (w/w) Lipozyme TLIM lipase, which managed to give 60 % yields of P-MLCT. Up scaled results in stirred tank batch reactor gave similar yields as lab scale. A 20 % increase in P-MLCT yield was obtained via RSM. The effect of enzymatic interesterification on the physicochemical properties of PKO:PO (90:10 w/w) were also studied. Thermoprofile showed that the P-MLCT oil melted below body temperature of 37 °C.

Mycelium-bound lipase from a locally isolated strain of Geotrichum candidum.

Mycelium-bound lipase (MBL), from a locally isolated Geotrichum candidum strain, was produced and characterized as a natural immobilized lipase. A time course study of its lipolytic activity in 1 L liquid broth revealed the maximum MBL activity at 4 h for mycelium cells harvested after 54 h. The yield and specific activity of MBL were 3.87 g/L dry weight and 508.33 U/g protein, respectively, while less than 0.2 U/mL lipase activity was detected in the culture supernatant. Prolonged incubation caused release of the bound lipase into the growth medium. The growth pattern of G. candidum, and production and properties of MBL were not affected by the scale. The stability of mycelia harboring lipase (MBL), harvested and lyophilized after 54 h, studied at 4 °C depicted a loss of 4.3% and 30% in MBL activity after 1 and 8 months, while the activity of free lipase was totally lost after 14 days of storage. The MBL from G. candidum displayed high substrate selectivity for unsaturated fatty acids containing a cis-9 double bond, even in crude form. This unique specificity of MBL could be a direct, simple and inexpensive way in the fats and oil industry for the selective hydrolysis or transesterification of cis-9 fatty acid residues in natural triacylglycerols.

Thermo-Switchable Enzyme@Metal-Organic Framework for Selective Biocatalysis and Biosensing.

The stimulus-responsive regulation of enzyme catalytic activity and selectivity provides a new opportunity to extend the functionality and efficiency of immobilized enzymes. This work aims to design and synthesize a thermo-switchable enzyme@MOF for size-selective biocatalysis and biosensing through the immobilization of Candida rugosa lipase (CRL) within ZIF-8 functionalized with thermally responsive polymer, poly(N-isopropylacrylamide) (PNIPAM) (CRL@ZIF-8-PNIPAM). Unlike free CRL, which does not demonstrate substrate selectivity, we can reversibly tune the pore size of the ZIF-8-PNIPAM nanostructures (open pores or blocked pores) through temperature stimulus and subsequently modulate the substrate selectivity of CRL@ZIF-8-PNIPAM. CRL@ZIF-8-PNIPAM had the highest hydrolytic activity for small molecules (12 mM p-nitrophenol/mg protein/min, 4-nitrophenyl butyrate (p-NP Be)) and the lowest hydrolytic activity for large molecules (0.16 mM p-nitrophenol/mg protein/min, 4-nitrophenyl palmitate (p-NP P)). In addition, CRL@ZIF-8-PNIPAM demonstrated thermo-switchable behavior for large molecules (p-NP P). The p-NP P hydrolytic activity of CRL@ZIF-8-PNIPAM was significantly lower at 40 °C (blocked pores) than at 27 °C (open pores). However, the transition of blocked pores and open pores is a gradual process that resulted in a delay in the "thermo-switchable" catalytic behavior of CRL@ZIF-8-PNIPAM during thermal cycling. CRL@ZIF-8-PNIPAM was also successfully used for the fabrication of electrochemical biosensors for the selective biosensing of pesticides with different molecular sizes.

Nonconventional Technologies in Lipid Modifications.

Lipid modifications play a crucial role in various fields, including food science, pharmaceuticals, and biofuel production. Traditional methods for lipid modifications involve physical and chemical approaches or enzymatic reactions, which often have limitations in terms of specificity, efficiency, and environmental impact. In recent years, nonconventional technologies have emerged as promising alternatives for lipid modifications. This review provides a comprehensive overview of nonconventional technologies for lipid modifications, including high-pressure processing, pulsed electric fields, ultrasound, ozonation, and cold plasma technology. The principles,mechanisms, and advantages of these technologies are discussed, along with their applications in lipid modification processes. Additionally, the challenges and future perspectives of nonconventional technologies in lipid modifications are addressed, highlighting the potential and challenges for further advancements in this field. The integration of nonconventional technologies with traditional methods has the potential to revolutionize lipid modifications, enabling the development of novel lipid-based products with enhanced functional properties and improved sustainability profiles.

Optimal binary solvent extraction system for phenolic antioxidants from mengkudu (Morinda citrifolia) fruit.

Antioxidants have been widely used in the food industry to enhance product quality by preventing oxidation of susceptible substances. This work was carried out to maximise the recovery of total phenolic content (TPC), total flavonoid content (TFC), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radical-scavenging capacity and 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging capacity from Morinda citrifolia fruit via modification of the ethanol concentration, extraction time and extraction temperature at minimal processing cost. The optimised conditions yielded values of 881.57 ± 17.74 mg GAE/100 g DW for TPC, 552.53 ± 34.16 mg CE/100 g DW for TFC, 799.20 ± 2.97 µmol TEAC/100 g DW for ABTS and 2,317.01 ± 18.13 µmol TEAC/100 g DW for DPPH were 75% ethanol, 40 min of time and 57 °C. The four responses did not differ significantly (p > 0.05) from predicted values, indicating that models obtained are suitable to the optimisation of extraction conditions for phenolics from M. citrifolia. The relative amounts of flavonoids were 0.784 ± 0.01 mg quercetin/g of extract and 1.021 ± 0.04 mg rutin/g of extract. On the basis of the results obtained, M. citrifolia extract can be used as a valuable bioactive source of natural antioxidants.

Open-label, single-arm, single-center clinical study on the effectiveness and safety of a moisturizer containing tocotrienol-rich composition in children with mild to moderate atopic dermatitis.

BACKGROUND: Little is known about antioxidant efficacy of topical vitamin E on atopic dermatitis (AD) due to lack of controlled clinical studies. AIM: The study evaluates the effectiveness and safety of a topical moisturizer containing tocotrienol-rich composition over 12 weeks on patients aged between 1 month and 12 years with mild to moderate AD. METHODS: We conducted a 12 weeks, prospective, open-label clinical study on the effect of tocotrienol as an adjunct to conventional treatment. This study was approved by the Ethics Committee for Research Involving Human Subject. JKEUPM-2019-274 (NMMR-19-1588-49234). RESULTS: Thirty AD patients with a mean age of 2.77 ± 3.05 were enrolled in the study. At week-12, significant reduction of investigator global assessment (63.4%), Patient-Oriented Scoring Atopic Dermatitis Index (PO-SCORAD) (65%), and SCORAD (52.3%) was noted (p < 0.05). There was also a significant decreased in pruritus intensity (46%, p < 0.05). Similarly at week-12, Infant's Dermatitis Quality of Life Index and Children's Dermatology Life Quality Index were found to improve significantly compared to baseline (p < 0.05). Instrumental assessment revealed improvement in TEWL and erythema index, 49.7% and 17.4%, respectively. No adverse reaction was observed. 95% of patients were satisfied with the moisturizer and 90% perceived it to be better than the one in the market. There was a 55.07% reduction in the use of hydrocortisone 1% cream toward the end of the study (p < 0.05). CONCLUSIONS: The results suggested that tocotrienol-rich moisturizer is safe and effective in the management of AD in young children.

Susceptibility to SARS-CoV-2 omicron following ChAdOx1 nCoV-19 and BNT162b2 versus CoronaVac vaccination.

The emergence of SARS-CoV-2 variants raises concerns of reduced COVID-19 vaccine efficacy. We investigated the humoral immunity in uninfected and previously infected ChAdOx1 nCoV-19, BNT162b2 and CoronaVac vaccinees, who have received complete regimes of vaccines by means of a SARS-CoV-2 surrogate virus blocking test. The ChAdOx1 nCoV-19 (p = 0.0013) and BNT162b2 (p = 0.0005) vaccines induced significant higher blocking activity with longer durability against the Spike (S) protein receptor binding domain (RBD) of wild type SARS-CoV-2 than the CoronaVac vaccine in uninfected vaccinees. Prior infection improved protection in the CoronaVac vaccinees. Subsequent investigation on the breadth of SARS-CoV-2 vaccine-induced antibody blocking responses, revealed that all vaccine platforms cross-protected uninfected vaccinees against all variant of concerns, except Omicron. Prior infection protected the ChAdOx1 nCoV-19 and BNT162b2 vaccinees against Omicron but not CoronaVac vaccinees. Our study suggests that vaccines that induce broader sterilizing immunity are essential to fight against fast-emerging variants.

In-vitro and in-vivo evaluations of tocotrienol-rich nanoemulsified system on skin wound healing.

Proper wound healing is vital for the survival of higher organisms. Responses to skin injury can lead to complications such as scar formation that can affect the quality of life. In this study, keratinocytes migration (scratch assay) and zebrafish tail regeneration experiments were used to evaluate the wound healing effect of a tocotrienol-based nanoemulsified (NE) system against ascorbic acid and phosphate-buffered saline (PBS) as positive and negative controls, respectively. MTT assay provided a concentration range of 0.35-8.75 µg/ml of nanoemulsion that produced cell viability more than 100%. After 24 hours of treatment, the wound closure of keratinocytes were found to be significantly faster by 73.76%, 63.37% and 35.56%, respectively when treated with 3.50 µg/ml and 1.75 µg/ml of NE compared to the blank. The lethal concentration at 50% (LC50 value) obtained from acute and prolonged toxicity was almost similar, which was 4.6 mg/ml and 5.0 mg/ml, respectively. Growth of zebrafish tail regeneration treated with NE at a concentration of 2.5 mg/ml was significantly faster than the untreated zebrafish, which regenerated to 40% on the fifth day, more than 60% on the tenth day of treatment and fully recovered at the twentieth day. In conclusion, these results showed the potential of the tocotrienols-based nanoemulsified system in enhancing wound healing through accelerated wound closure.

W/O high internal phase emulsion featuring by interfacial crystallization of diacylglycerol and different internal compositions.

High internal phase emulsions (HIPEs) show promising application in food and cosmetic industries. In this work, diacylglycerol (DAG) was applied to fabricate water-in-oil (W/O) HIPEs. DAG-based emulsion can hold 60% water and the emulsion rigidity increased with water content, indicating the water droplets acted as "active fillers". Stable HIPE with 80% water fraction was formed through the combination of 6 wt% DAG with 1 wt% polyglycerol polyricinoleate (PGPR). The addition of 1 w% kappa (κ)-carrageenan and 0.5 M NaCl greatly reduced the droplet size and enhanced emulsion rigidity, and the interfacial tension of the internal phase was reduced. Benefiting from the Pickering crystals-stabilized interface by DAG as revealed by the microscopy and enhanced elastic modulus of emulsions with the gelation agents, the HIPEs demonstrated good retaining ability for anthocyanin and ß-carotene. This study provides insights for the development of W/O HIPEs to fabricate low-calories margarines, spread or cosmetic creams.

Phospholipidomics of bovine milk subjected to homogenization, thermal treatment and cold storage.

Milk processing technology disrupts milk fat globule membrane (MFGM) structures and decreases the phospholipid content in MFGM. The present study aimed to evaluate the effects of homogenization, thermal treatment, and cold storage on milk phospholipids. A total of 175 phospholipid molecular species were identified and quantified. Phosphatidylcholine was the most abundant phospholipid, and sphingomyelin accounted for only a small amount of phospholipid in bovine milk. In addition, a total of 37 plasmalogens (167.5 µg/mL) were identified in bovine milk with lysophosphatidylcholine plasmalogen being the most abundant. Processing technologies decreased the phospholipid content with both boiled and frozen milk demonstrating the highest reduction. Compared to raw milk, only 70% of phospholipid remained in frozen milk. Both S-plot and volcano-plot showed that heat treatment and subsequent cold storage decreased the phosphatidylserine and lysophospholipid contents.

Selective antibacterial activities and storage stability of curcumin-loaded nanoliposomes prepared from bovine milk phospholipid and cholesterol.

Present study prepared curcumin-loaded nanoliposomes using bovine milk, krill phospholipids and cholesterol; and investigated the effects of cholesterol on membrane characteristics, storage stability and antibacterial properties of the curcumin nanoliposomes. Bovine milk phospholipids which have higher saturation than krill phospholipids resulted in formation of curcumin-loaded nanoliposomes with higher encapsulation efficiency (84.78%), larger absolute value of zeta potential and vesicle size (size: 159.15 ± 5.27 nm, zeta potential: -28.3 ± 0.62 mV). Cholesterol helps to formation of a more hydrophobic, compact and tighter bilayer membrane structure which improved the storage stability of nanoliposomes under alkaline (66.25 ± 0.46%), heat (43.25 ± 0.69%) and sunlight (49.44 ± 1.78%) conditions. In addition, curcumin-loaded nanoliposomes can effectively target infectious bacteria which secrete pore-forming toxins such as Staphylococcus aureus by causing the bacterial cell wall to lysis. Findings from present work can guide future development of novel antibacterial agents for use in food preservation.

Production of a solvent, detergent, and thermotolerant lipase by a newly isolated Acinetobacter sp. in submerged and solid-state fermentations.

The lipase production ability of a newly isolated Acinetobacter sp. in submerged (SmF) and solid-state (SSF) fermentations was evaluated. The results demonstrated this strain as one of the rare bacterium, which is able to grow and produce lipase in SSF even more than SmF. Coconut oil cake as a cheap agroindustrial residue was employed as the solid substrate. The lipase production was optimized in both media using artificial neural network. Multilayer normal and full feed forward backpropagation networks were selected to build predictive models to optimize the culture parameters for lipase production in SmF and SSF systems, respectively. The produced models for both systems showed high predictive accuracy where the obtained conditions were close together. The produced enzyme was characterized as a thermotolerant lipase, although the organism was mesophile. The optimum temperature for the enzyme activity was 45°C where 63% of its activity remained at 70°C after 2 h. This lipase remained active after 24 h in a broad range of pH (6-11). The lipase demonstrated strong solvent and detergent tolerance potentials. Therefore, this inexpensive lipase production for such a potent and industrially valuable lipase is promising and of considerable commercial interest for biotechnological applications.

Biomimetic self-assembly of lipase-zeolitic imidazolate frameworks with enhanced biosensing of protox inhibiting herbicides.

Protox inhibiting herbicides such as nitrofen have detrimental effects on the environment and human health. The current work aims to fabricate a Candida rugosa lipase (CRL)-based electrochemical sensor for rapid and sensitive detection of protox inhibiting herbicides (nitrofen). We proposed the use of poly(vinylpyrrolidone) (PVP) and amino-acids to promote accumulation of Zn2+ ions at the surfaces of Candida rugosa lipase (CRL) and subsequently induce self-assembly of a CRL-zeolitic imidazolate framework (ZIF) structure. This process can be easily and rapidly achieved via a one-pot facile self-assembly method. Steady-state fluorescence spectroscopy indicated that CRL has undergone a conformational change following encapsulation within the ZIF structure. This conformational change is beneficial as the prepared PVP/Glu/CRL@ZIF-8 exhibited enhanced catalytic activity (207% of native CRL), and higher substrate affinity (lower Km than native CRL) and showed high stability under harsh denaturing conditions. PVP/Glu/CRL@ZIF-8 was finally used for electrochemical biosensing of nitrofen. The fabricated biosensor has a wide linear detection range (0-100 µM), a lower limit of detection and a good recovery rate.