Unequivocal Enantiomeric Identification and Analysis of 10 Chiral Pesticides in Fruit and Vegetables by QuEChERS Method Combined With Liquid Chromatography‐Quadruple/Linear Ion Trap Mass Spectrometry Determination

In this research, 10 chiral pesticides in fruits and vegetables were simultaneously determined using chiral liquid chromatography triple quadrupole‐linear ion trap hybrid mass spectrometry (LC‐QqLIT). The QuEChERS method was applied for sample preparation, and an enhanced product ion (EPI) scan was used to acquire tandem mass spectrometry (MS/MS) spectra for the library search. Parameters including limit of detection (LOD), limit of quantification (LOQ), linearity, relative standard deviation (RSD), and matrix effects were evaluated in five representative matrices (strawberry, leek, cowpea, tomato, and eggplant). Good linearity with coefficient of determination (r²) ≥0.997 was obtained for all 20 enantiomers in these five matrices over the range from 1.0 to 250 µg L^‐1. All the recoveries at 5 and 50 µg kg^‐1 (n = 5) ranged between 70% and 120% with RSD below 20%, indicating satisfactory precision. The LOQ for the enantiomers ranged between 0.05 and 1 µg kg^‐1. Based on the proposed method, 135 commonly consumed fruits and vegetables taken from markets in Guizhou province, China, were analyzed. Enantioselective degradation for the selected chiral pesticides was observed in most of the positive samples. Chirality 27:958–964, 2015. © 2015 Wiley Periodicals, Inc.     

Effect on lycopene, β-carotene,ascorbic acid and phenolic content in tomato fruits infected by Alternaria alternata and its toxins (TeA,AOH and AME)

Tomato is considered as one of the most important sources of nutrients such as lycopene, β-carotene, flavonoids, ascorbic acid (vitamin C) and hydroxyl-cinnamic acid derivatives. The quality and quantity of nutrients in tomato fruits were decreased during the severe infection of Alternaria alternata. The present study deals with the estimation of lycopene, β-carotene, phenolic and ascorbic acid content in tomato fruits which were infected with A. alternata and its toxins such as tenuazonic acid (TeA), alternariol (AOH) and alternariol monomethyl ether (AME). The lycopene, β-carotene, ascorbic acid and phenolic content were found lowest in pathogen-infected fruits i.e. (0.66 ± 0.03 mg/g), (0.14 ± 0.01 mg/g), (1.89 ± 0.2 mg/g) and (0.58 ± 0.05 mg/g), respectively, followed by toxins-treated samples as compared to the control. The results concluded that A. alternata mostly affects the nutritional values of tomato fruits due to the combined effect of the toxins.     

Efficacy of some biorational insecticides against Tuta absoluta (Meyrick) (Lepidoptera: Gelechiidae) under laboratory and greenhouse conditions in Kuwait

The tomato leafminer, Tuta absoluta, is one of the most destructive pests of tomato worldwide. Management of the pest is mainly based on chemical insecticides. Reliance on insecticides is difficult to sustain because of unintended long‐term adverse effects on the environment and human health. Consequently, there is a need to develop pest management strategies that ensure the production of high‐quality products, while at the same time ensuring environmental sustainability and maximum consumer protection. We evaluated the efficacy the biopesticides: Azadirachtin, Bacillus thuringiensis, Steinernema feltiae and Beauveria bassiana individually and in combination against T. absoluta under laboratory and greenhouse conditions. When second instar larvae were exposed to tomato leaf discs treated with Azadirachtin (3 g / L), B. thuringiensis (0.5 g/L) or B. bassiana (1.5 g/L), 70%–86%, 55%–65%, and 45.5%–58.5% mortality was observed, respectively. Steinernema feltiae (1,000 IJs/ml) was the least effective biopesticide, with 26%–42% mortality. In the greenhouse trials on tomato, pest infestation (mines/10 leaves/plant) and fruits damaged were significantly lower on plants treated with Azadirachtin  +  B. thuringiensis or Azadirachtin  +  B. bassiana compared to plants treated with Azadirachtin, B. thuringiensi, B. bassiana or S. feltiae alone. Azadirachtin  +  B. thuringiensis and Azadirachtin  +  B. bassiana resulted in 90% and 81% reduction in fruits damaged in the summer experiments, respectively, and 96% and 91% in winter. The most severe pest infestation was observed on plants treated with S. feltia. The results indicate that the biopesticides, except S. feltia, can contribute to T. absoluta control in greenhouse tomato crops. In particular, the combined use of Azadirachtin with B. thuringiensis or B. bassiana provided the highest level of control of the pest. The potential for including these biopesticides in an overall sustainable integrated pest management programme for T. absoluta is discussed.     

The efficacy of high and low volume spray applications of Mimic® (tebufenozide) for managing autumn gum moth larvae Mnesampela privata (Lepidoptera: Geometridae) in eucalypt plantations

Abstract 1 The autumn gum moth Mnesampela privata (Guenée) (Lepidoptera: Geometridae, Ennominae) is a native moth that can outbreak, resulting in significant defoliation of plantation eucalypts in southern Australia. 2 Laboratory trials tested M. privata larvae for their dose–response to the ecdysone agonist, Mimic® 700 WP (a.i. 700 g/kg tebufenozide); ground and aerial field trials also tested its efficacy in eucalypt plantations. 3 The laboratory trials showed that there was no significant difference in mortality between larvae treated with 172 g Mimic® (120 g a.i)/ha and those sprayed with doses ranging from 86 to 3340 g Mimic®/ha. 4 Laboratory and field trials demonstrated that second instars were the most susceptible, with the most rapid response. However, second to fourth instars all reached 100% and fifth instars 90% mortality 3 weeks after aerial spraying at 120 g a.i./ha. 5 Aerial spraying an Eucalyptus globulus plantation with 120 g a.i. Mimic® at 20 L/ha caused 95% mortality of instars two to five, and 100% for instars two to four within 3 weeks after spraying. 6 Ground spraying to run‐off with 120 g a.i. Mimic®/ha reduced defoliation of E. grandis from between 67% to 80% for unsprayed trees to 0% defoliation for sprayed trees. 7 The window for effective management of M. privata larvae is 3–5 weeks, during first to third instar development. 8 Replacement of broad‐spectrum insecticides with the more target‐specific Mimic® should increase the biodiversity of plantations and therefore would be more environmentally friendly.     

Control of Tuta absoluta (Meyrick) (Lepidoptera: Gelechiidae) in greenhouse tomato crops using the mating disruption technique

The effectiveness of mating disruption to control the tomato leafminer, Tuta absoluta (Meyrick) (Lepidoptera: Gelechiidae), in greenhouse tomato crops was evaluated in four trials carried out in winter–spring and summer–winter growing seasons in Southwestern Sardinia (Italy). Pheromone dispensers loaded with 60 mg of the natural blend of the major and minor sex pheromone component (rate 90 : 10) were applied in disrupted greenhouses at a rate of 1000/ha (60 g of active ingredient/ha). Male captures in monitoring pheromone traps, percentage of tomato plants infested by T. absoluta and damage on leaves and fruits were monitored weekly and compared in disrupted and untreated (control) greenhouses. In greenhouses disrupted with 1000 dispensers/ha, a reduction of 93–97% in male trap captures was observed, compared with control. Leaf damage was significantly lower in greenhouses disrupted with 1000 dispensers/ha than in control ones, with a reduction of infestation throughout the growing season ranging from 57% to 85%. Pheromone dispensers applied at the density of 1000/ha significantly reduced the percentage of damaged fruits by 62–89%. In control greenhouses, the highest damage on leaves and fruits was generally observed in edge plants, while leaf and fruit infestation was uniformly distributed in pheromone‐treated greenhouses, indicating an even distribution of the pheromone cloud inside the greenhouse. Mating disruption showed to be an efficient strategy to control in greenhouse the tomato leafminer and can be included in the overall tomato integrated pest management programs.     

Anticonvulsant Activity of Enantiomeric N‐trans‐Cinnamoyl Derivatives of 2‐Aminopropan‐1‐ols and 2‐Aminobutan‐1‐ols

Epilepsy, one of the most frequent neurological disorders, is still insufficiently treated in about 30% of patients. As a consequence, identification of novel anticonvulsant agents is an important issue in medicinal chemistry. In the present article we report synthesis, physicochemical, and pharmacological evaluation of N‐trans‐cinnamoyl derivatives of R and S‐2‐aminopropan‐1‐ol, as well as R and S‐2‐aminobutan‐1‐ol. The structures were confirmed by spectroscopy and for derivatives of 2‐aminopropan‐1‐ols the configuration was evaluated by means of crystallography. The investigated compounds were tested in rodent models of seizures: maximal electroshock (MES) and subcutaneous pentetrazol test (scPTZ), and also in a rodent model of epileptogenesis: pilocarpine‐induced status prevention. Additionally, derivatives of 2‐aminopropan‐1‐ols were tested in benzodiazepine‐resistant electrographic status epilepticus rat model as well as in vitro for inhibition of isoenzymes of cytochrome P450. All of the tested compounds showed promising anticonvulsant activity in MES. For R(–)‐(2E)‐N‐(1‐hydroxypropan‐2‐yl)‐3‐phenylprop‐2‐enamide pharmacological parameters were found as follows: ED₅₀ = 76.7 (68.2–81.3) mg/kg (MES, mice i.p., time = 0.5 h), ED₅₀ = 127.2 (102.1–157.9) mg/kg (scPTZ, mice i.p., time = 0.25 h), TD₅₀ = 208.3 (151.4–230.6) mg/kg (rotarod, mice i.p., time = 0.25 h). Evaluation in pilocarpine status prevention proved that all of the reported compounds reduced spontaneous seizure activity and act as antiepileptogenic agents. Both enantiomers of 2‐aminopropan‐1‐ols did not influence cytochrome P450 isoenzymes activity in vitro and are likely not to interact with CYP substrates in vivo. Chirality 28:482–488, 2016. © 2016 Wiley Periodicals, Inc.     

Economic injury level and crop loss assessment for Tuta absoluta (Lepidoptera: Gelechiidae) on different tomato cultivars

Specifying the relationship between pests and their host plants in terms of damage is one of the basic concepts of integrated pest management (IPM) programmes. The crop loss and economic injury level (EIL) of Tuta absoluta (Lepidoptera: Gelechiidae) were determined on different tomato cultivars using gain threshold (field experiment) and regression (semi‐field experiment) methods. By assessing the crop loss in 2015 and 2016, four out of seven infested tomato cultivars had a significant yield loss in terms of weight of total fruits versus the control under the open‐field conditions. However, the total number of tomato cultivars had no significant difference to control treatment. The semi‐field experiment included six treatments (0, 2, 4, 6, 8 and 10 gravid females/plant) and examined two tomato cultivars. The tomato cages with between 6 and 10 gravid females/plant showed the highest number and weight of damaged fruits. Based on pesticide control costs, the market value of tomato and the control efficacy, we determined the EIL for T. absoluta. In the field experiment, the EIL value for T. absoluta on “Petomech,” “Cal JN3,” “Rio Grande” and “Early Urbana Y” cultivars was 4.15, 4.47, 4.70 and 5.04 larvae per plant, respectively. Based on regression equations, we calculated the EIL values for T. absoluta on “Cal JN3” and “Early Urbana Y” to be 4.75 and 5.44 larvae/plant, respectively. Crop loss assessment and EIL are necessary components of cost‐effective IPM programs and can be effective tools for making decisions about the application of pesticides against T. absoluta.     

Enantioselective Degradation of (2RS,3RS)‐Paclobutrazol in Peach and Mandarin Under Field Conditions

In this study we investigated the enantioselective degradation of (2RS,3RS)‐paclobutrazol in peach and mandarin fruits under field conditions after foliar treatment at 500 mg active ingredient/L using a Lux Cellulose‐1 chiral column on a reverse‐phase liquid chromatography–tandem mass spectrometry system. Degradations of paclobutrazol in both fruits followed first‐order kinetics, with half‐lives of about 9 days. Initial deposits were 1.63 mg/kg on peach and 1.99 mg/kg on mandarin; terminal concentrations were lower than 0.05 mg/kg, which was acceptable in most cases. As anticipated, paclobutrazol levels in peels of mature mandarin were about 6.3 times higher than in pulp, indicating the potential risk of peel consumption. We also observed that paclobutrazol degradation in mature mandarin was relatively slow, indicating it might not be efficient enough to hold mandarin fruits on trees for lowering paclobutrazol concentrations. Significant enantioselectivity was observed: the (2R,3R)‐enantiomer was preferentially degraded in mandarin (whole fruit, peels, and pulp) but enriched in peach. Because of its more rapid degradation in mandarin and the lower levels observed in pulp compared with peels, potential endocrine‐related side effects due to the (2R,3R)‐enantiomer pose less of a risk in mandarin than in peach. Chirality 26:400–404, 2014. © 2014 Wiley Periodicals, Inc.     

Enantioselective Degradation and Chiral Stability of Metalaxyl‐M in Tomato Fruits

Metalaxyl is an important chiral acetanilide fungicide, and the activity almost entirely originates from the R‐enantiomer. Racemic metalaxyl has been gradually replaced by the enantiopure R‐enantiomer (metalaxyl‐M). In this study a chiral residue analysis method for metalaxyl and the metabolite metalaxyl acid was set up based on high‐performance liquid chromatography tandem mass spectroscopy (HPLC‐MS/MS). The enantioselective degradation and chiral stability of metalaxyl‐M in tomato fruits in two geographically distinct regions of China (Heilongjiang and Hunan Province) were evaluated and the enantioselectivity of metalaxyl acid was also investigated. Tomato plants grew under field conditions with a one‐time spray application of metalaxyl‐M wettable powder. It was found that R‐metalaxyl was not chirally stable and the inactive S‐metalaxyl was detected in tomato fruits. At day 40, S‐metalaxyl derived from R‐metalaxyl accounted for 32% and 26% of the total amount of metalaxyl, respectively. The metabolites R‐metalaxyl acid and S‐metalaxyl acid were both observed in tomato, and the ratio of S‐metalaxyl acid to the sum of S‐ and R‐metalaxyl acid was 36% and 28% at day 40, respectively. For both metalaxyl and metalaxyl acid, the half‐life of the S‐enantiomer was longer than the R‐enantiomer. The results indicated that the enantiomeric conversion should be considered in the bioactivity evaluation and environmental pollution assessment. Chirality 28:382–386, 2016. © 2016 Wiley Periodicals, Inc.     

Intake of fruits and vegetables in relation to 10-year weight gain among Spanish adults

Objective: Despite the alarming increase in the prevalence of obesity, epidemiologic studies that prospectively examine the fruit and vegetable consumption and other lifestyle factors in relation to weight gain (WG) are still insufficient. We explored the associations between fruit and vegetable intake and WG over a 10‐year period in an adult Mediterranean population. Methods and Procedures: We performed a 10‐year follow‐up study with healthy participants (n = 206) aged 15–80 years at baseline in 1994, who participated in a nutrition survey in Valencia, Spain. Data on diet, lifestyle factors, and body weight were obtained in 1994 and 2004 using a food frequency questionnaire (FFQ) and direct measurements. Results: The average WG over the study period was 3.41 (s.d. 6.9) kg. In multivariate analyses, participants in the third quartile of fruit intake at baseline in 1994 had lower risk of WG ≥ 3.41 kg compared to those in the lowest quartile (oddsratio (OR) = 0.31, 95% confidence interval (CI), 0.11–0.85; P trend = 0.044). Regarding vegetable intake, the risk of WG was lowest in participants of the fourth quartile (>333 g/day), which had an 84% reduced risk of gaining 3.41 kg weight (OR = 0.18, 95% CI, 0.05–0.66; P trend = 0.017). When the intake of fruits and vegetables was combined, the risk of WG decreased across quartiles, with the lowest risk among those in the fourth quartile (OR = 0.22, 95% CI, 0.06–0.81; P trend = 0.022). Further adjustment for an increased intake of fruits and vegetables over the past 10 years reported by participants in 2004 did not appreciably alter the observed ORs. Discussion: Dietary patterns associated with a high intake of fruits and vegetables in Mediterranean populations may reduce long‐term risk of subsequent WG and obesity among adults.     

Continuous fermentation to produce xanthan biopolymer: Effect of dilution rate

Single-stage continuous fermentations to produce xanthan gum have been run at dilution rates (D) from 0.023 to 0.196 hr^?1. Xanthan production rate (XPR) was a function of D. XPR increased from 0.34 g/hr/kg at D = 0.023 hr^?1 to the maximum 0.84 g/hr/kg at D = ca. 0.15 hr^?1. At D > 0.15 hr^?1 XPR decreased and at the highest D studied (0.196 hr^?1) was 0.69 g/hr/kg. Yield of xanthan from glucose consumed was 81–89%. Steady states ended between 6.5 and 8.7 turnovers when a variant strain occurred.     

Stand type is more important than red wood ant abundance for the structure of ground‐dwelling arthropod assemblages in managed boreal forests

• 1 The relationships between red wood ants (Formica rufa group) and other ground‐dwelling arthropods were studied in young managed forests stands in Eastern Finland. The main objectives were: (i) to test the influence of stand type (dominant tree species; age: sapling versus pole stage) and numbers of red wood ants on the occurrence of other ground‐dwelling arthropods and (ii) to study the occurrence of red wood ants versus other arthropods on a distance gradient from ant mounds. We used pitfall traps set in 5–14‐year‐old sapling stands and 30–45‐year‐old pole‐stage stands of Scots pine (Pinus sylvestris L.) and birch (Betula spp.) forests.
• 2 Pitfall trap catches of red wood ants did not vary significantly between the forest stand types, although some groups of other arthropods showed clear responses to stand type (e.g. catches of other Formicinae and Gnaphosidae were higher in sapling stands than in pole‐stage stands). The number of red wood ants clearly explained less of the variation in assemblages of other ground‐dwelling arthropods than the forest stand type.
• 3 Red wood ant numbers decreased significantly with distance from the mounds, but the other ground‐dwelling arthropods were insensitive to this gradient or even showed a preference for proximity to ant mounds and high ant activity.
• 4 The results obtained in the present study suggest that wood ants do not have strong effects on several other ground‐dwelling arthropod groups in young managed forests other than in the immediate vicinity of their mounds.

     

Integrating cultural control methods for tomato late blight (Phytophthora infestans) in Uganda

Cultural control measures against tomato late blight (Phytophthora infestans) were evaluated in six field experiments over 3 years in Uganda. Each experiment included sanitation (removal of diseased plant tissues), fungicide (mancozeb) application, and an untreated control, as standard treatments. Late blight incidence and severity were greatly reduced by sanitation, without reducing the number of healthy leaves; however, tomato growth and production were adversely affected. Fungicide treated plants retained the highest numbers of flowers and attached fruits and gave the highest yields. Three cultural practices were evaluated in repeated experiments for their effectiveness in alleviating the adverse effects of sanitation. Tomatoes grown within plastic shelters early in the production cycle were taller, and had more healthy leaves than those grown late. The numbers of diseased leaves and disease severity were equally low in sanitation alone and plastic shelter/with sanitation treatments. Flower and fruit production were significantly higher when tomatoes were grown under early shelters with sanitation than with sanitation alone. Planting density was increased without significant effects on late blight and tomato growth and production. Intercropping tomato with soybean (Glycine max) or sesame (Sesamum indicum), with sanitation, limited late blight development, but taller intercrops suppressed tomato growth and production. Integrated treatments (combining plastic shelters, a sesame intercrop and high tomato planting density) were evaluated, with and without sanitation, against the fungicide mancozeb. The mean numbers of healthy leaves in the integrated treatments were not significantly less than with fungicide treatment. Late blight incidence and severity were higher in the integrated plots without than with sanitation. The numbers of flowers and attached fruits were not significantly less in integrated treatments than in fungicide treated plots, but tomato yield was highest with fungicide treatment.     

A Solanum neorickii introgression population providing a powerful complement to the extensively characterized Solanum pennellii population

We present a complementary resource for trait fine‐mapping in tomato to those based on the intra‐specific cross between cultivated tomato and the wild tomato species Solanum pennellii, which have been extensively used for quantitative genetics in tomato over the last 20 years. The current population of backcross inbred lines (BILs) is composed of 107 lines derived after three backcrosses of progeny of the wild species Solanum neorickii (LA2133) and cultivated tomato (cultivar TA209) and is freely available to the scientific community. These S. neorickii BILs were genotyped using the 10K SolCAP single nucleotide polymorphism chip, and 3111 polymorphic markers were used to map recombination break points relative to the physical map of Solanum lycopersicum. The BILs harbor on average 4.3 introgressions per line, with a mean introgression length of 34.7 Mbp, allowing partitioning of the genome into 340 bins and thereby facilitating rapid trait mapping. We demonstrate the power of using this resource in comparison with archival data from the S. pennellii resources by carrying out metabolic quantitative trait locus analysis following gas chromatography–mass spectrometry on fruits harvested from the S. neorickii BILs. The metabolic candidate genes phenylalanine ammonia‐lyase and cystathionine gamma‐lyase were then tested and validated in F₂ populations and via agroinfiltration‐based overexpression in order to exemplify the fidelity of this method in identifying the genes that drive tomato metabolic phenotypes.     

Nematicidal screening of essential oils and potent toxicity of Dysphania ambrosioides essential oil against Meloidogyne incognita in vitro and in vivo

It is known that some plant essential oils have pesticide activities. Among the 29 oils evaluated in this study, 14 showed nematicidal activities of 8 to 100% at the concentration of 1,000 μg/ml, compared with a control of 0.01 g/ml Tween 80^®. At a lower concentration of 500 μg/ml, only Dysphania ambrosioides oil caused >90% mortality of second‐stage juveniles (J2) of Meloidogyne incognita. The LC₅₀ and LC₉₅ values for D. ambrosioides oil were 307 μg/ml and 580 μg/ml, respectively. M. incognita eggs placed in D. ambrosioides oil solutions had a significant reduction in J2 hatching compared with controls. Therefore, the oil had a toxic effect on both eggs and J2 of M. incognita. This was in contrast to nematicides on the market that act efficiently only on J2. When J2 were placed in D. ambrosioides oil at its LC₅₀ concentration and inoculated onto tomato plants, the reduction in numbers of galls and eggs was 99.5% and 100%, respectively. Dysphania ambrosioides oil applied to the potting substrate of plants at a concentration of 1,100 μg/ml significantly reduced the number of galls and eggs of M. incognita, whereas a concentration of 800 μg/ml only reduced the number of eggs compared with the controls (Tween 80^® and water). The main components of the D. ambrosioides oil detected by gas chromatography–mass spectrometry were (Z)‐ascaridole (87.28%), E‐ascaridole (8.45%) and p‐cymene (3.35%), representing 99.08% of the total oil composition. Given its nematicidal activity, D. ambrosioides oil represents an exciting raw material in the search for new bioactive molecules for the pesticide industry.