Radical scavenging activity and metabolomic profiling study of ylang-ylang essential oils based on high-performance thin-layer chromatography and multivariate statistical analysis.

Ylang-ylang (YY) essential oil (EO) is distilled from the fresh-mature flowers of the Annonaceae family tropical tree Cananga odorata [Lam.] Hook. f. & Thomson, and is widely used in perfume and cosmetic industries for its fragrant character. Herein, two different metabolomic profiles obtained using high-performance thin-layer chromatography (HPTLC), applying different stains, namely 2,2-diphenyl-1-picrylhydrazyl (DPPH·) and p-anisaldehyde, were used for discrimination of 52 YY samples across geographical origins and distillation grades. The first profile is developed using the DPPH· stain based on the radical scavenging activity (RSA) of YY EOs. Results of the HPTLC-DPPH· assay confirmed that RSA of YY EOs is in proportion to the length of distillation times. Major components contributing to the RSA of YY EOs were tentatively identified as germacrene D and α-farnesene, eugenol and linalool, by gas chromatography-mass spectrometry (GC-MS) and GC-flame ionisation detector (GC-FID). The second profile was developed using the general-purpose p-anisaldehyde stain based on the general chemical composition of YY EOs. Untargeted metabolomic discrimination of YY EOs from different geographical origins was performed based on the HPTLC-p-anisaldehyde profiles, followed by principal component analysis (PCA). A discrimination and prediction model for identification of YY distillation grade was developed using PCA and partial least squares regression (PLS) based on binned HPTLC-ultraviolet (254 nm) profiles, which was successfully applied to distillation grade determination of blended YY Complete EOs.

Chemical, physical, and functional properties of Thai indigenous brown rice flours.

Thai indigenous brown rice flours from Nakhon Si Thammarat, Thailand, namely Khai Mod Rin (KMRF) and Noui Khuea (NKRF), were assessed for quality aspects in comparison with brown Jasmine rice flour (JMRF) and commercial rice flour (CMRF) from Chai Nat 1 variety. All the rice flours had different chemical composition, physical characteristic, and techno-functionality. The KMRF, NKRF, and JMRF were classified as a low amylose type (19.56-21.25% dw). All rice flours had low total extractable phenolic content (0.1-0.3 mg GAE/g dw) with some DPPH● scavenging activity (38.87-46.77%). The variations in the bulk density (1.36-1.83 g/cm3), water absorption capacity (0.71-1.17 g/g), solubility (6.93-13.67%), oil absorption capacity (1.39-2.49 g/g), and swelling power (5.71-6.84 g/g) were noticeable. The least gelation concentration ranged from 4.0 to 8.0% where KMRF was easier to form gel than JMRF, and NKRF/CMRF. The foam capacity of the flours was relatively low (1.30-2.60%). The pasting properties differed among rice flours and the lowest pasting temperature was observed in CMRF. Overall, the chemical, physical, functional, and pasting qualities of flours were substantially influenced by rice variety. The findings offered fundamental information on Thai indigenous rice flour that can be used in food preparations for specific uses.

The Impact of Formulation on the Content of Phenolic Compounds in Snacks Enriched with Dracocephalum moldavica L. Seeds: Introduction to Receiving a New Functional Food Product.

A new type of multigrain snack has been designed containing varied additions of Moldavian dragonhead (Dracocephalum moldavica L.) seeds. The antioxidant properties and the general health benefits of this plant material have already been widely acknowledged. The research discussed herein aimed to investigate the influence of the formulation and expansion method (frying) on the content of polyphenolic compounds, individual phenolic acids, and antiradical properties of innovative snacks enriched with dragonhead seeds. The highest content of polyphenols (0.685 mg GAE/mL), free phenolic acids (47.052 µg/g of dry matter), and highest radical scavenging activity (96.23% towards DPPH) were found in the fried snacks enriched with 22% of seeds. In these samples, 11 phenolic acids were detected. Strong positive correlations were seen between the addition of dragonhead and the polyphenol content (r = 0.989) and between the quantity of the enriching additive and the content of free phenolic acids (r = 0.953). The research has shown that such innovative snacks have the potential to supply health-benefiting free phenolic acids, e.g., salicylic, isoferulic, ferulic, p-coumaric, vanillic. Our studies provide an introduction to the development of a new range of functional foods.

A Eu(III)-based Metal Organic Framework: Selective Sensing of Picric Acid and Nursing Application Values On the Cerebral Edema Induced by Cerebral Hemorrhage Via Reducing the Coagulation Factor II Activity.

A new three-dimensional lanthanide metal-organic framework (Ln-MOF), [Eu4(L)4(H2O)8]·10H2O (1, H3L = biphenyl-3'-nitro-3,4',5-tricarboxylic acid), has been constructed via solvothermal technology and its framework has been detected by the single-crystal X-ray diffraction and elemental analyses. Complex 1 with typical emission of Eu3+ ion represents dramatic luminescence quenching affect for picric acid (PA) and the linear Stern-Volmer plot was surveyed in the consistence, ranging from 0.05 to 0.15 mM (Ksv = 98,074 M- 1). Its therapeutic effect of the compound on the cerebral edema caused by cerebral hemorrhage was estimated and the mechanism was explored. Possible binding interactions have been investigated by molecular docking simulations, from which the binding interactions are identified and the carboxyl oxygens are responsible for those identified interactions.

Facile Microwave-Assisted Synthesis of Functionalized Carbon Nitride Quantum Dots as Fluorescence Probe for Fast and Highly Selective Detection of 2,4,6-Trinitrophenol.

Functionalized carbon nitride quantum dots (CNQDs) are fabricated by moderate carbonization of L-tartaric acid and urea in oil acid media by a facile microwave-assisted solvothermal method. The obtained CNQDs are monodispersed with a narrow size distribution (average size of 3.5 nm), and exhibit excellent selectivity and sensitivity of fluorescence quenching for 2,4,6-trinitrophenol (TNP) with a quenching efficiency coefficient Ksv of 4.75 × 104 M-1. This sensing system exhibits a fast response time within 1 min and a wide linear response range from 0.1 to 15 µM. The limit of detection is as low as 87 nM, which is comparable or lower than the other probes. The application of the developed probe to the detection of TNP in spiked water samples yields satisfactory results. The mechanism of fluorescence quenching is also discussed. Graphical Abstract An optical sensor based on functionalized carbon nitride quantum dots (CNQDs) were fabricated from L-tartaric acid and urea by a facile one-pot microwave-assisted solvothermal method, and were effectively utilized to the detection of 2,4,6-trinitrophenol (TNP) based on fluorescence (FL) quenching.

Targeted isolation of 1,1-diphenyl-2-picrylhydrazyl inhibitors from Saxifraga atrata using medium- and high- pressure liquid chromatography combined with online high performance liquid chromatography-1,1-diphenyl-2- picrylhydrazyl detection.

Traditional Tibetan medicine (TTM) is a valuable source of novel therapeutic lead molecules inspired by natural products (NPs). The health benefits of Saxifraga atrata are well documented in TTM, but reports on its chemical composition are limited, most likely due to the complicated purification process. Herein, target separation and identification of 4 main radical scavenging compounds from the methanolic extract of S. atrata was were performed using medium- and high-pressure liquid chromatography coupled with online HPLC-DPPH detection. The sample was pretreated using medium pressure liquid chromatography with MCI GELⓇ CHP20P styrene-divinylbenzene beads as a stationary phase, yielding 1.4 g of the target DPPH inhibitors (Fr4, 11.9% recovery). The compounds were further purified and isolated using HPLC on RP-C18 (ReproSil-Pur C18 AQ) followed by HILIC (Click XIon) column separation, resulting in 2.8 mg of fraction Fr4-1-1, 6.8 mg of fraction Fr4-2, 244.9 mg of the Fr4-3-1 sample, and 38.3 mg of Fr4-4-1. The structure and purity of the target compounds were determined, and four compounds (ethyl gallate, 11-O-galloylbergenin, rutin and isoquercitrin) were isolated with >95% purity. The developed methodology is efficient for targeted isolation of high-purity radical scavengers from NP extracts and could be used for rapid identification and isolation of DPPH inhibitors from various NPs.

A facile and rapid approach to synthesize uric acid-capped Ti3C2 MXene quantum dots for the sensitive determination of 2,4,6-trinitrophenol both on surfaces and in solution.

Herein, uric acid@Ti3C2 quantum dots (UA@Ti3C2 QDs) were synthesized via a microwave-assisted strategy on the basis of acid etching and stripping. The UA@Ti3C2 QDs have bright blue emission. Intriguingly, the fluorescence emission of the UA@Ti3C2 QDs was significantly quenched after the addition of 2,4,6-trinitrophenol (TNP), due to inner-filter effect (IFE). Based on these findings, a novel environmentally friendly and water-soluble fluorescence probe based on UA@Ti3C2 QDs was demonstrated for the sensitive and selective detection of TNP. The method presented a wide linear range for TNP detection in the 0.01-40 µM range, with a low detection limit of 9.58 nM. Furthermore, the probe was successfully used for the sensitive detection of TNP in real water and smartphone-based colorimetric (SPBC) detection of TNP on surfaces with the linear range from 10.0 to 100.0 ng. On the whole, this work provides an effective strategy for the synthesis of UA@Ti3C2 QDs and an alternative fluorescence probe for detecting TNP both on surface and in solution.

Aggregation-directed High Fidelity Sensing of Picric Acid by a Perylenediimide-based Luminogen.

Widespread use of picric acid (PA) in chemical industries and deadly explosives poses dreadful impact on all living creatures as well as the natural environment and has raised global concerns that necessitate the development of fast and efficient sensing platforms. To address this issue, herein, we report a perylenediimide-peptide conjugate, PDI-1, for detection of PA in methanol. The probe displays typical aggregation caused quenching (ACQ) behaviour and exhibits a fluorescence "turn-off" sensory response towards PA which is unaffected by the presence of other interfering nitroaromatic compounds. The sensing mechanism involves PA induced aggregation of the probe into higher order tape like structures which leads to quenching of emission. The probe possesses a low detection limit of 5.6 nM or 1.28 ppb and a significantly high Stern-Volmer constant of 6.87×104  M-1 . It also exhibits conducting properties in the presence of PA vapours and thus represents a prospective candidate for vapour phase detection of PA. This is, to the best of our knowledge, the first example of a perylenediimide based probe that demonstrates extremely specific, selective and sensitive detection of PA and thus grasps the potential for application in practical scenarios.

Phytochemical Characterization and In Vitro Antioxidant Properties of Four Brassica Wild Species from Italy.

In the present study, we evaluated for the first time the variability of antioxidant traits of four Brassica wild species: B. incana, B. macrocarpa, B. villosa, and B. rupestris. The content of the main water-soluble antioxidants (phenolics, ascorbic acid, and total biothiols) and the in vitro antioxidant potential (1,1-diphenyl-2-picrylhydrazil (DPPH) and superoxide anion scavenging capacity) were investigated. A total of 28 polyphenolic compounds were identified by LC/MS and quantitated by HPLC/DAD analysis. Kaempferol and quercetin derivatives were the most abundant phenolics compared to hydroxycinnamoyl gentiobiosides. In the ten populations, phenolics ranged from 163.9 to 533.9 mg/100 g dry weight (d.w.), ascorbic acid from 7.6 to 375.8 mg/100 g d.w., and total biothiols from 0.59 to 5.13 mg/100 g d.w. The different classes of phytochemicals were separated using solid-phase extraction at increasing methanol concentrations, and the antioxidant power of fractionated extracts was evaluated. The superoxide anion scavenging activity was significantly correlated to phenolics, particularly to flavonol derivatives, while DPPH was mainly related to ascorbic acid content. The present findings improve the knowledge of the phytochemical composition of Italian Brassica wild species by showing the great diversity of phytochemicals among populations and highlighting their importance as a valuable genetic resource for developing new cultivars with improved bioactive content.

Zn(II)-Based Coordination Polymer for Detection of Picric Acid in Aqueous Media and Treatment Effect against Deep Vein Thrombosis by Reducing P-ERK2 and p53 Expression.

The coordination polymers based on Zn(II) ions and the metal nodes which has chemical formula of {[Zn3(L)2(tib)2(H2O)2]·(DMF)2}n (1) was synthesized via using 1,3,5-tris(1-imidazolyl)benzene (tib) and 2,6-di(4-carboxylphenyl)pyridine-4-carboxylic acid (H3L) as ligands under solvothermal conditions. Given its strong luminescent emission at room temperature and the uncoordinated N-donor sites in the framework, the selective detection performance of 1 toward the nitroanalytes was studied, 1's sensitive fluorescence quenching reactions along with selectivity to the electron-deficient TNP over other analytes of nitro within the aqueous phase was studied via the method of fluorescence quenching titration. Furthermore, the treatment effect of the compound on the deep vein thrombosis (DVT) was evaluated. Firstly, the ELISA was carried out to determine IL-17A content. Then, the platelet function was determined via the western blot by measuring expression level of platelet activation signaling pathway protein p-ERK2 and p53.

Nitrogen/sulfur-co-doped carbon quantum dots: a biocompatible material for the selective detection of picric acid in aqueous solution and living cells.

Here, a fast and eco-friendly one-pot hydrothermal technique is utilized for the synthesis of nitrogen/sulfur-co-doped fluorescent carbon quantum dots (NS-CQDs) from a simple precursor of citric acid (CA) and thiosemicarbazide (TSC). The obtained NS-CQDs exhibited strong blue emission under UV light, with fluorescence quantum yield (QY) of ~37.8%. The Commission internationale de l'eclairage (CIE) coordinates originated at (0.15, 0.07), which confirmed the blue fluorescence of the synthesized NS-CQDs. Interestingly, the prepared NS-CQDs were successfully used as a selective nanoprobe for the monitoring of environmentally hazardous explosive picric acid (PA) in different nitro- and non-nitro-aromatic derivatives of PA. The mechanism of the NS-CQDs was also explored, and was posited to occur via the fluorescence resonance electron transfer (FRET) process and non-fluorescent complex formation. Importantly, this system possesses excellent biocompatibility and low cytotoxicity in HeLa cervical cancer cells; hence, it can potentially be used for PA detection in analytical, environmental, and pathological applications. Furthermore, the practical applicability of the proposed sensing system to pond water demonstrated the feasibility of our system along with good recovery. Graphical abstract.

Luminescent Coordination Polymer for Picric Acid Detection and Treatment on Spinal Cord Injury Model Via Upregulating the trka Expression.

A luminescent coordination polymer based on Tb(III) has been synthesized with the tripodal carboxylic acid ligand containing N,O codonors (H2PBA = 5-[4-pyridin-3-yl-benzoylamino]-isophthalic acid) as ligand under solvothermal conditions. The chemical formula of this polymer is {[Tb2(PBA)3(H2O)3]·DMF·3H2O}n (1). Complex 1 has good sensitivity and selectivity to picric acid (PA). At 0-30 µmol/L, 1's quenching constant is 4.5 × 104 L/mol. In the biological function study, the motor function of spinal cord-injured animals after different treatments was evaluated using the blood-brain barrier (BBB) method. The trka expression level on the neural stem cells after treatment was measured to reveal the underlying mechanism.

Selective determination of 2,4,6-trinitrophenol by using a novel carbon nanoparticles as a fluorescent probe in real sample.

2,4,6-Trinitrophenol (TNP) is widely used in our daily life; however, excessive use of TNP can lead to a large number of diseases. Therefore, it is necessary to find an effective method to detect TNP. Herein, the rapid fluorescence quenching by TNP was developed for the fluorometric determination of TNP in aqueous medium based on the internal filter effect. Nitrogen-sulfur-codoped carbon nanoparticles (N,S-CNPs), synthesized by a one-pot solvothermal method with the precursors of L-cysteine and citric acid, were applied for the determination of TNP as a fluorescent probe. The excitation peak center of N,S-CNPs and the emission peak center are 340 nm and 423 nm, respectively. The probe can be used in a variety of conditions to detect TNP due to its relatively stable properties. Meanwhile, it has a fast response time (< 1 min), wide linear response range (0.1-40 µM), and low detection limit (43.0 nM). This probe still has excellent selectivity and high sensitivity. The method was also used to detect standard water samples with a satisfactory recovery rate, and it will be used in the application of pollutants and clinical diseases. Graphical abstract.

Multi-sensing function integrated nitrogen-doped fluorescent carbon dots as the platform toward multi-mode detection and bioimaging.

In this work, nitrogen-doped carbon dots (N-CDs) were successfully utilized as a photoluminescent platform for multi-mode sensing of chromium(VI) [Cr(VI)], 2,4,6-trinitrophenol (TNP) and ascorbic acid (AA). The N-CDs with green fluorescent emission were synthesized via one-pot method using p-phenylenediamine and ammonia as precursors. The structure and optical properties were characterized by Fourier transform infrared spectroscopy, ultraviolet visible spectroscopy and fluorescence spectroscopy, respectively. Cr(VI) and TNP were able to absorb the excitation band and emission band of N-CDs and decreased the photoluminescence of N-CDs from internal filtration effect (IFE). Besides, the construction of N-CDs/Cr(VI) mixture can implement as a fluorescence platform for further detection of AA on the basis of the oxidation-reduction reactions between Cr(VI) and AA. Meanwhile, as-prepared N-CDs exhibit strong photostability, low toxicity and great biocompatibility. Moreover, the as-fabricated N-CDs have been smoothly achieved bioimaging in SMMC7721 cells owing to its low toxicity. It is prospective that N-CDs can be applied as a rapid multi-function sensing platform to biosensing and biomedical optical imaging.

A highly sensitive and selective detection of picric acid using fluorescent sulfur-doped graphene quantum dots.

The development of an analytical probe to monitor highly mutagenic picric acid (PA) carries enormous significance for the environment and for health. A novel, simple and rapid fluorescence analytical assay using sulfur-doped graphene quantum dots (SGQDs) was designed for the highly sensitive and selective detection of PA. SGQDs were synthesized via simple pyrolysis of 3-mercaptopropionic acid and citric acid and characterized using advanced analytical techniques. Fluorescence intensity (FI) of SGQDs was markedly quenched by addition of PA, attributed to the inner filter effect and dominating static quenching mechanism between the two, in addition to a significant colour change. The calibration curve of the proposed assay exhibited a favourable linearity between quenched FI and PA concentration over the 0.1-100 µΜ range with a lowest detection limit of 0.093 µΜ and a correlation coefficient of 0.9967. The analytical assay was investigated for detection of trace amounts of PA in pond and rain water samples and showed great potential for practical applications with both acceptable recovery (98.0-100.8%) and relative standard deviation (1.24-4.67%). Analytical performance of the assay in terms of its detection limit, linearity range, and recovery exhibited reasonable superiority over previously reported methods, thereby holding enormous promise as a simple, sensitive, and selective method for detection of PA.

Amphiphilic gemini-iridium (III) complex for rapid and selective detection of picric acid in water and intracellular.

Inspired by the structure and properties of gemini surfactant, a novel amphiphilic gemini-iridium complex (GIC-Ir) has been developed, which can spontaneously form vesicles by self-assembly and exhibit excellent dispersibility and high emission intensity in water. The emission of GIC-Ir can be rapidly and selectively quenched by picric acid (PA) due to the aromatic groups and two long-chain quaternary ammonium (QA) groups with positive charge, which endow GIC-Ir vesicles outstanding capability to capture negatively charged PA, and greatly promote the interaction between GIC-Ir and PA. Theoretical calculations and spectral studied indicated that the photoinduced electron transfer and resonance energy transfer may be responsible to the emission quenching. Furthermore, the real water samples and in vitro studies further prove that GIC-Ir can be used as a promising chemosensor for the detection of PA both in water and intracellular.

A Facilely Synthesized Dual-State Emission Platform for Picric Acid Detection and Latent Fingerprint Visualization.

To achieve a highly efficient, dual-state emission platform for picric acid (PA) detection and latent fingerprint (LFP) visualization, flexible alkyl chains have been facilely attached to the commercial organic dye 3,4,9,10-perylenetetracarboxylic dianhydride to provide the target perylenetetracarboxylate molecules PTCA-C4, PTCA-C6, and PTCA-C12. Interestingly, all these molecules exhibited impressive fluorescence characteristics with high photoluminescence quantum yields (PLQYs) of around 93.0 % in dilute solution. Also, emissive features were observed in the solid state because close molecular packing is prevented by the alkyl chains, especially for PTCA-C6, which has a high PLQY value of 49.0 %. Benefiting from its impressive fluorescence performance in both solution and as aggregates, PTCA-C6 was used as a dual-state emission platform for PA detection and also LFP visualization. For example, double-responsive fluorescence quenching in solution was observed in PA detection studies, resulting in high quenching constants (KSV ) and also low limit-of-detection values. Furthermore, the fingerprint powder based on PTCA-C6 also presented an impressive performance on various substrates in terms of fluorescence intensity and resolution, clearly providing the specific fine details of latent fingerprints. These results demonstrate that the facilely synthesized PTCA-C6 with efficient dual-state emission exhibits great potential in the real-world applications of PA detection and LFP visualization.

Dissecting the Potential of Selenoproteins Extracted from Selenium-Enriched Rice on Physiological, Biochemical and Anti-Ageing Effects In Vivo.

Ageing is an irreversible phenomenon and the processes which can delay it are under consideration for a long time by the scientific community. Selenium is an important candidate for it, but the impact of selenoprotein on nutritional changes and ageing has not been reported well. In this regard, antioxidant activities and free radical scavenging effect of selenoproteins extracted from selenium-rich rice were studied. Mice were administered a subcutaneous abdominal injection of D-galactose to induce the ageing model and fed with different selenoprotein dosage diet. Deviations among biochemical activities (total antioxidant capacity (T-AOC), glutathione peroxidase (GSH-Px), superoxide dismutase (SOD) and malondialdehyde (MDA)) in liver and serum of the mice were assessed. The degree of liver injury, antioxidant genes and protein relative expression were estimated. The protein content, selenium content, hydroxyl scavenging and DPPH radicals were accessed in selenoprotein components. The selenoprotein constituent had protein and selenium contents in different components as water-soluble proteins > alkali-soluble proteins > salt-soluble proteins > ethanol-soluble proteins. The enzymatic activity (total antioxidant capacity, GSH-Px and SOD) in liver and serum of mice was significantly enhanced in selenoprotein diet groups. D-Galactose-induced liver injury was significantly reduced by selenoprotein diet of 25 µg/(kg day). Real-time qPCR and Western blot disclosed the enhanced relative expression of antioxidant genes (SOD2, GPX1, TrxR2 and Nrf2) and HO-1 protein in the positive control (Vc) and selenoprotein diet groups. In conclusion, selenoprotein treatment was found to have a positive influence on liver hepatocytes and biochemical features in mice. It might be used as a potential diet in scavenging oxidative injury and supporting enzymatic antioxidant system.

Comparative study of Cl,N-Cdots and N-Cdots and application for trinitrophenol and ClO- sensor and cell-imaging.

To understand the effect of Cl doping in carbon dots, nitrogen-doped carbon dots (N-Cdots) and nitrogen and chlorine dual-doped carbon dots (Cl,N-Cdots) were fabricated by high-temperature carbonization and low-temperature concentrated acid (HCl) acidification of dried shaddock peel, respectively. The quantum yield of Cl,N-Cdots is about four times of that of N-Cdots and the size of Cl,N-Cdots is smaller than that of N-Cdots. Furthermore, since trinitrophenol (PA) and ClO- could effectively quench the fluorescence of Cl,N-Cdots, the fluorescence sensors for determining PA and ClO- was constructed, respectively. The linear range of PA and ClO- are 0.9-90 µM and 3.24-216 µM with the limit of detection of 37.1 nM and 2.88 µM, respectively. The proposed sensor was used to detect PA in Taiyuan tap water, Wutai tap water, Wutai rain water and Wutai river water samples with encouraging results. The as-constructed sensor was also used to detect ClO- in Taiyuan tap water and commercial disinfectants. Last but not least, Cl,N-Cdots was employed as an agent for A549 and HeLa cell-imaging, possessing optimal imaging effect and ultra-low cytotoxicity. Our results suggested that Cl,N-Cdots has promising applications in sensing, water monitoring, commodity supervision and cell-imaging.

The BODIPY-Based Chemosensor for Fluorometric/Colorimetric Dual Channel Detection of RDX and PA.

A fluorometric/colorimetric dual-channel chemosensor based on a hydrazine-substituted BODIPY probe has been successfully fabricated for the detection of RDX and PA. The chemosensor displays turn-on fluorescence behavior upon RDX with a detection limit of 85.8 nM, while showing a turn-off response to PA with a detection limit of 0.44 µM. Meanwhile, an obvious color difference is observed by the naked-eye after the reaction for RDX. Thus, in application, a two-to-two logic gate is constructed for potential application in explosives detection. Additionally, portable equipment is also developed for in situ determination of RDX.