Multifunctional Metal-Organic Framework (MOF)-Based Nanoplatforms for Crop Protection and Growth Promotion.

Phytopathogen, pest, weed, and nutrient deficiency cause severe losses to global crop yields every year. As the core engine, agrochemicals drive the continuous development of modern agriculture to meet the demand for agricultural productivity and increase the environmental burden due to inefficient use. With new advances in nanotechnology, introducing nanomaterials into agriculture to realize agrochemical accurate and targeted delivery has brought new opportunities to support the sustainable development of green agriculture. Metal-Organic frameworks (MOFs), which weave metal ions/clusters and organic ligands into porous frameworks, have exhibited significant advantages in constructing biotic/abiotic stimuli-responsive nanoplatforms for controlled agrochemical delivery. This review emphasizes the recent developments of MOF-based nanoplatforms for crop protection, including phytopathogen, pest, and weed control, and crop growth promotion, including fertilizer/plant hormone delivery. Finally, forward-looking perspectives and challenges on MOF-based nanoplatforms for future applications in crop protection and growth promotion are also discussed.

A Lesion Microenvironment-Responsive Fungicide Nanoplatform for Crop Disease Prevention and Control.

Controlled fungicide delivery in response to the specific microenvironment produced by fungal pathogens is an advisable strategy to improve the efficacy of fungicides. Herein, the authors construct a smart fungicide nanoplatform, using mesoporous silica nanoparticles (MSNs) as nanocarriers loaded with eugenol (EU) and Ag+ coordinated polydopamine (Ag+ -PDA) as a coating to form Ag+ -PDA@MSNs-EU NPs for Botrytis cinerea (B. cinerea) control. As a botanical fungicide, EU offers an eco-friendly alternative to synthetic fungicides and can upregulate several defense-related genes in the tomato plant. The Ag+ -PDA coating can lock the EU inside the nanocarriers and respond to the oxalic acid produced by B. cinerea to corelease the loaded EU and Ag+ . The results demonstrate that Ag+ -PDA@MSNs-EU NPs can effectively inhibit the mycelial growth of B. cinerea on detached and potted tomato leaves. The construction of such a smart fungicide nanoplatform provides new guidance to design controlled fungicides release systems, which can respond to the microenvironment associated with plant pathogen to realize fungus control.

Accurate Identification of Degraded Products of Aflatoxin B1 Under UV Irradiation Based on UPLC-Q-TOF-MS/MS and NMR Analysis.

Analysis, purification, and characterization of AFB1 degraded products are vital steps for elucidation of the photocatalytic mechanism. In this report, the UPLC-Q-TOF-MS/MS technique was first coupled with purification and NMR spectral approaches to analyze and characterize degraded products of AFB1 photocatalyzed under UV irradiation. A total of seventeen degraded products were characterized based on the UPLC-Q-TOF-MS/MS analysis, in which seven ones (1-7) including four (stereo) isomers (1,2, 5, and 6) were purified and elucidated by NMR experiments. According to the structural features of AFB1 and degraded products (1-7), the possible photocatalytic mechanisms were suggested. Furthermore, AFB1 and degraded products (1-7) were evaluated against different cell lines. The results indicated that the UPLC-Q-TOF-MS/MS technique combined with purification, NMR spectral experiments, and biological tests was an applicable integrated approach for analysis, characterization, and toxic evaluation of degraded products of AFB1, which could be used to evaluate other mycotoxin degradation processes.

MOF-based multi-stimuli-responsive supramolecular nanoplatform equipped with macrocycle nanovalves for plant growth regulation.

Controllable and on-demand delivery of agrochemicals such as plant hormones is conducive to improving agrochemicals utilization, tackling water and environmental pollution, reducing soil acidification, and realizing the goals of precision agriculture. Herein, a smart plant hormone delivery system based on metal-organic frameworks (MOFs) and supramolecular nanovalves, namely gibberellin (GA)-loaded CLT6@PCN-Q, is constructed through supramolecular host-guest interaction to regulate the growth of dicotyledonous Chinese cabbage and monocotyledonous wheat. The porous nanoscale MOF (NMOF) with a uniform diameter of 97 nm modified by quaternary ammonium (Q) stalks is served as a cargo reservoir, followed by the decoration of carboxylated leaning tower[6]arene (CLT6) based nanovalves on NMOF surfaces through host-guest interactions to fabricate CLT6@PCN-Q with a diameter of ∼101 nm and a zeta potential value of -13.2 mV. Interestingly, the as-fabricated supramolecular nanoplatform exhibits efficient cargo loading and multi-stimuli-responsive release under various external stimuli including pH, temperature, and competitive agent spermine (SPM), which can realize the on-demand release of cargo. In addition, GA-loaded CLT6@PCN-Q is capable of effectively promoting the seeds germination of wheat and stem growth of dicotyledonous Chinese cabbage and monocotyledonous wheat (1.86 and 1.30 times of control groups, respectively). The smart supramolecular nanoplatform based on MOFs and supramolecular nanovalves paves a way for the controlled delivery of plant hormones and other agrochemicals for promoting plant growth, offering new insights and methods to realize precision agriculture. STATEMENT OF SIGNIFICANCE: To achieve controllable and sustainable release of cargos such as agrochemicals, a smart MOF-based multi-stimuli-responsive supramolecular nanoplatform equipped with supramolecular nanovalves was fabricated via the host-guest interaction between quaternary ammonium stalks-functionalized nanoMOFs and water-soluble leaning tower[6]arene. The as-prepared supramolecular nanoplatform with uniform diameter distribution demonstrated good cargo release in response to various external stimuli. The installation of synthetic macrocycles could effectively reduce cargo loss in the pre-treatment process. This type of supramolecular nanoplatform exhibited good promoting effect on seed germination and plant growth dicotyledonous Chinese cabbage and monocotyledonous wheat. As an eco-friendly, controlled, and efficient cargo delivery system, this supramolecular nanoplatform will be a promising candidate in precision agriculture and controlled drug release to attract the broad readership.

Supramolecular Nanoplatform Based on Mesoporous Silica Nanocarriers and Pillararene Nanogates for Fungus Control.

Synthetic fungicides have been widely used to protect crops from fungal diseases. However, excessive use of synthetic fungicides leads to the generation of fungicide resistance in fungal pathogens. Recently, smart cargo delivery systems have been introduced for the construction of a pesticide delivery nanoplatform, benefiting from their controlled release performance. Herein, a fungal pathogen microenvironment-responsive supramolecular fungicide nanoplatform has been designed and constructed, using quaternary ammonium salt (Q)-modified mesoporous silica nanoparticles (MSN-Q NPs) as nanocarriers loaded with berberine hydrochloride (BH) and carboxylatopillar[5]arene (CP[5]A) as nanogates to form BH-loaded CP[5]A@MSN-Q NPs for effective inhibition of Botrytis cinerea. CP[5]A as nanogates can endow the fungicide nanoplatform with pH stimuli-responsive release features for the control of fungicide release. The loaded BH, as a natural plant fungicide, provides an ecofriendly alternative to synthetic fungicides for controlling B. cinerea. Interestingly, we use oxalic acid (OA) secreted by B. cinerea as a trigger so that BH can be released from the fungicide nanoplatform on demand under pathogen microenvironments for controlling B. cinerea. The experimental results indicate that the fabricated fungicide nanoplatform could effectively inhibit the mycelial growth and spore germination, providing a new way for the management of B. cinerea in actual application.

Eco-Friendly Nanoplatforms for Crop Quality Control, Protection, and Nutrition.

Agricultural chemicals have been widely utilized to manage pests, weeds, and plant pathogens for maximizing crop yields. However, the excessive use of these organic substances to compensate their instability in the environment has caused severe environmental consequences, threatened human health, and consumed enormous economic costs. In order to improve the utilization efficiency of these agricultural chemicals, one strategy that attracted researchers is to design novel eco-friendly nanoplatforms. To date, numerous advanced nanoplatforms with functional components have been applied in the agricultural field, such as silica-based materials for pesticides delivery, metal/metal oxide nanoparticles for pesticides/mycotoxins detection, and carbon nanoparticles for fertilizers delivery. In this review, the synthesis, applications, and mechanisms of recent eco-friendly nanoplatforms in the agricultural field, including pesticides and mycotoxins on-site detection, phytopathogen inactivation, pest control, and crops growth regulation for guaranteeing food security, enhancing the utilization efficiency of agricultural chemicals and increasing crop yields are highlighted. The review also stimulates new thinking for improving the existing agricultural technologies, protecting crops from biotic and abiotic stress, alleviating the global food crisis, and ensuring food security. In addition, the challenges to overcome the constrained applications of functional nanoplatforms in the agricultural field are also discussed.

Bioactive metabolites from the desert plant-associated endophytic fungus Chaetomium globosum (Chaetomiaceae).

Globosumin, an undescribed chromene-4,7(4aH)-dione-tetramic acid PKS-PKS-NRPS hybrid, and globosumone, an undescribed azaphilone, together with ten known metabolites, were isolated from the desert plant-associated endophytic fungus Chaetomium globosum (Chaetomiaceae). The planar structures and relative configurations of globosumin and globosumone were determined by high-resolution ESI-MS and NMR data, and the absolute configurations of these two metabolites were determined by electronic circular dichroism (ECD) and circular dichroism (CD) combined with time-dependent density functional theory (TDDFT)-based quantum-chemical calculations. Chaetoglobosin A displayed biological effects against the seedling growth of Arabidopsis thaliana (Brassicaceae) in a dose-dependent manner, and this compound also exhibited biological activity against two cancer cell lines, A549 and HepG2, with IC50 values of 6.82 ± 2.34 and 38.62 ± 7.44 µM, respectively.

Stereochemical determination of four 10-membered ring resorcylic acid lactones from the desert plant endophytic fungus Chaetosphaeronema hispidulum.

Four 10-membered ring resorcylic acid lactones (RALs) including a new compound hispidulactone F (1) and three known analogs hispidulactone B (2), 2 R, 4R-sonnerlactone (3), and 2 R, 4S-sonnerlactone (4) were isolated from the special bioenvironmental desert plant endophytic fungus Chaetosphaeronema hispidulum. The structure of the new compound hispidulactone F (1) was determined by extensive spectra analysis including HR-ESI-MS, NMR (1H, 13C, 1H-1H COSY, HSQC, and HMBC). Hispidulactone F (1) and hispidulactone B (2) were a pair of stereoisomers at C-3, whereas 2 R, 4R-sonnerlactone (3) and 2 R, 4S-sonnerlactone (4) were another pair of stereoisomers at C-4. The stereochemistries of the hydroxyl groups at C-3 in 1 and 2, and at C-4 in 3 and 4 were first determined by modified Mosher's reactions. Thus, the absolute configuration C-3 in hispidulactone B (2) was not right in our previous report, and was rectified to be R. Compounds 1 and 4 were evaluated for their cytotoxic effects on the proliferation of HepG2. The possible biosynthetic pathway of compounds 1-4 was also presented.

Cytotoxic Activity of Inositol Angelates and Tirucallane-Type Alkaloids from Amoora Dasyclada.

Three new inositol angelate compounds (1-3) and two new tirucallane-type alkaloids (4 and 5) were isolated from the Amoora dasyclada, and their structures were established mainly by means of combination of 1D and 2D nuclear magnetic resonance and HR-ESI-MS. Based on cytotoxicity testing, compounds 4 and 5 exhibited significant cytotoxic activity against human cancer cell line HepG2 with IC50 value at 8.4 and 13.2 µM. In addition, compounds 4 and 5 also showed remarkable growth inhibitory activity to Artemia salina larvae.

Diagnostically analyzing 1H NMR spectra of sub-types in chaetoglobosins for dereplication.

1H-NMR spectra provide abundant diagnostic information including chemical shift values, splitting patterns, coupling constants, and integrals. Thus some key functional groups, and even planar structures could be elucidated on the basis of carefully analyzing the corresponding 1H NMR spectrum. In this paper, the different sub-types of chaetoglobosins are classified according to the structural features, of which the 1H NMR spectra are systematically summed up. Thus diagnostically analyzing the 1H-NMR spectra could identify possible sub-types of chaetoglobosins, which could be used for dereplication. According to the analysis of this report, it implies that different new sub-types or new sub-type combinations in the key skeleton of chaetoglobosins might exist in nature. More importantly, dereplication based on 1H NMR spectral analysis will not only provide a useful approach to determine the chaetoglobosins structures quickly, but also could set a good example for structural dereplication of other NPs.

Antioxidant phenolic compounds isolated from wild Pyrus ussuriensis Maxim. fruit peels and leaves.

Thirteen phenolic compounds were isolated from pear (Pyrus ussuriensis Maxim.) peels and leaves extracts by using various column chromatography techniques with a guided DPPH (1,1-diphenyl-2-picrylhydrazyl) radical-scavenging assay, the result of antioxidant activity of phenolic compounds is then verified by measurement of ROS (reactive oxygen species). The isolated compounds were identified as rutin (1), (-)-catechin (2), orobol (3), daidzein (4), tricin 4'-O-[threo-ß-guaiacyl-(7″-O-methyl)-glyceryl] ether (5), tricin 4'-O-[threo-ß-guaiacyl-(7″-O-methyl-9″-O-acetyl)-glyceryl] ether (6), 5,7,3',5'-tetrahydroxyflavanone (7), artselaeroside A (8), trilobatin (9), 3-(2,4,6-trihydroxyphenyl)-1-(4-hydroxyphenyl)-propan-1-one (10), quercetin-3-O-(3″-O-galloyl)-α-l-rhamnopyranoside (11), apigenin (12) and quercetin (13) on the basis of nuclear magnetic resonance spectroscopy along with comparison with literature data. Among these compounds, quercetin and quercetin-3-O-(3″-O-galloyl)-α-l-rhamnopyranoside exhibited potent DPPH radical-scavenging activity with IC50 (Half Maximal Inhibitory Concentration) value of 6.06 and 9.60µg/mL, respectively. The results revealed that P. ussuriensis could be used in the fields of food and medicine to prevent human aging diseases.

Identification of insecticidal constituents of the essential oils of Dahlia pinnata Cav. against Sitophilus zeamais and Sitophilus oryzae.

The aim of this research was to determine the chemical composition of the essential oils of Dahlia pinnata, their insecticidal activity against Sitophilus zeamais and Sitophilusoryzae and to isolate insecticidal constituents. Based on bioactivity-guided fractionation, active constituents were isolated and identified as D-limonene, 4-terpineol and α-terpineol. Essential oils and active compounds tested exhibited contact toxicity, with LD50 values ranging from 132.48 to 828.79 µg/cm(2) against S. zeamais and S. oryzae. Essential oils possessed fumigant toxicity against S. zeamais and S. oryzae with LC50 from 14.10 to 73.46 mg/L. d-Limonene (LC50 = 4.55 and 7.92 mg/L) showed stronger fumigant toxicity against target insects. 4-Terpineol (88 ± 8%) and d-limonene (87 ± 5%) showed the strongest repellency against S. zeamais and S. oryzae, respectively. The results indicate that essential oils and insecticidal constituents have potential for development into natural fumigants, insecticides or repellents for control of the stored-product insect pests.

Characterization of cytochalasins from the endophytic Xylaria sp. and their biological functions.

Bioassay-guided fractionation of the fermentation extract of Xylaria sp. XC-16, an endophyte from Toona sinensis led to the isolation of two new cytochalasans cytochalasin Z27, 1, and cytochalasin Z28, 2, along with three known compounds seco-cytochalasin E, 3, and cytochalasin Z18, 4, and cytochalasin E, 5. The structures of 1 and 2 were elucidated by spectroscopic and electronic circular dichroism methods. Compound 5 was shown to be potently cytotoxic against brine shrimp (LC50 = 2.79 µM), comparable to that of the positive agent toosendanin (LC50 = 4.03 µM), and also exhibited potential phytotoxic effects on Lactuca sativa and Raphanus sativus L. seedlings, which are higher than that of the positive control glyphosate. Additionally, the fungicidal effect of 2 against the phytopathogen Gibberella saubinetti was better than that of hymexazol. This is the first report of the three types of cytochalasins present in genus Xylaria. A structure-phytotoxicity activity relationship is also discussed.

Cytotoxic azaphilone alkaloids from Chaetomium globosum TY1.

Three novel azaphilone alkaloids, namely chaetomugilides A-C (1-3), together with three related compounds (4-6) were isolated from the methanol extract of Chaetomium globosum TY1, an endophytic fungus isolated from Ginkgo biloba. Their structures were elucidated on the basis of extensive 1D and 2D NMR as well as HRESI-MS spectroscopic data analysis. The isolated compounds exhibited highly cytotoxic activities against human cancer cell line HePG2 with the IC50 values range from 1.7 to 53.4µM.

Cloning and functional characterization of a caffeic acid O-methyltransferase from Trigonella foenum-graecum L.

A cDNA encoding an O-methyltransferase (namely FGCOMT1) was identified from the medicinal plant Trigonella foenum-graecum L. The FGCOMT1 enzyme is a functional caffeic acid O-methyltransferase (COMT) and is localized in the cytosol. Kinetic analysis indicated that FGCOMT1 protein exhibited the highest catalyzing efficiency towards 5-hydroxy ferulic acid and caffeic acid as substrates, but did not possess the abilities to methylate either quercetin or tricetin in vitro. Furthermore, transformation of Arabidopsis loss-of-function Atomt1 mutant with a FGCOMT1 cDNA partially complements accumulation of sinapoyl derivatives but did not function to produce the major methylated flavonol isorhamnetin in seeds. The results from this study indicated that FGCOMT1 is a COMT with substrate preference to monomeric lignin precursors but is not involved in the flavonoid methylation in T. foenum-graecum L.

Antioxidant hispidin derivatives from medicinal mushroom Inonotus hispidus.

Two natural antioxidants, named inonotusin A (1) and B (2), were isolated from the methanolic extract of the fruit bodies of Inonotus hispidus, together with (E)-4-(3,4-dihydroxyphenyl)but-3-en-2-one (3), hispidin (4) and 3,4-dihydroxybenzaldehyde (5). Their structures were identified by means of extensive NMR and MS data analysis. Compounds 1, 2 and 4 exhibited significant scavenging activity against the 2,20-azinobis(3-ethylbenzhiazoline-6-sulfonate) (ABTS) radical cation. Compound 1 also showed moderate cytotoxicity against a human breast carcinoma cell line (MCF-7) with IC(50) values of 19.6 µM.

Metabolic engineering of isoflavone genistein in Brassica napus with soybean isoflavone synthase.

Genistein, 4',5,7-trihydroxyisoflavone, is an isoflavonoid compound predominantly restricted to legumes and known to possess phyto-oestrogenic and antioxidative activities. The key enzyme that redirects phenylpropanoid pathway intermediates from flavonoids to isoflavonoids is the isoflavone synthase (IFS). Brassica napus is a non-legume oilseed crop with vegetative tissues producing phenylpropanoids and flavonoids, but does not naturally accumulate isoflavones due to the absence of IFS. To demonstrate whether exogenous IFS is able to use endogenous substrate to produce isoflavone genistein in oilseed crop, the soybean IFS gene (GmIFS2) was incorporated into B. napus plants. The presence of GmIFS2 in B. napus was shown to direct the synthesis and accumulation of genistein derivatives in leaves up to 0.72 mg g(-1) DW. In addition, expression levels for most B. napus genes in the phenylpropanoid pathway were altered. These results suggest that the heterologous GmIFS2 enzyme is functionally active at using the B. napus naringenin as a substrate to produce genistein in oilseed rape.

Cloning and functional characterization of a chalcone isomerase from Trigonella foenum-graecum L.

Flavonoids belong to a group of plant natural products with variable phenolic structures and play important roles in protection against biotic and abiotic stress. Fenugreek (Trigonella foenum-graecum L.) seeds and stems contain flavonol glycosides and isoflavone derivatives. Up to now, the molecular features of fenugreek flavonoid biosynthesis have not been characterized. Here we present cloning of a cDNA encoding a chalcone isomerase (namely TFGCHI-1) from the leaves of T. foenum-graecum which convert chalcones to flavanones in vitro. Transformation of Arabidopsis loss-of-function TT5 (CHI) mutant with a TFGCHI-1 cDNA complemented TT5 and produced higher levels of flavonol glycosides than wild-type Col-0.

Structure and absolute configuration of toxic polyketide pigments from the fruiting bodies of the fungus Cortinarius rufo-olivaceus.

Two new polyketide-derived pigments, named rufoolivacins B (), and D (), with a 4',10-coupled aryl linkage between polysubstituted 1-naphthol and 1,4- or 1,2-anthraquinone, together with nine known metabolites including rufoolivacins A () and C (), have been isolated from the fruiting bodies of the Chinese toadstool Cortinarius rufo-olivaceus (basidiomycetes). Their structures were characterized on the basis of spectroscopic methods, including 2D-NMR experiments (COSY, NOESY, HSQC, and HMBC). The axial chirality of and was assigned through analysis of their CD spectra and ZINDO and TDDFT calculations. Compounds and were found to be unusual natural products incorporating an ortho-anthraquinone chromophore. All the metabolites were shown to be toxic toward the brine shrimp.