Insecticidal and fungicidal activity of new synthesized chitosan derivatives

Chitosan, the N-deacetylated derivative of chitin, is a potential biopolysaccharide owing to its specific structure and properties. In this paper, we report on the synthesis of 24 new chitosan derivatives, N-alkyl chitosans (NAC) and N-benzyl chitosans (NBC), that are soluble in dilute aqueous acetic acid. The different derivatives were synthesized by reductive amination and analyzed by 1H NMR spectroscopy. A high degree of substitution (DS) was obtained with N-(butyl)chitosan (DS 0.36) at a 1:1 mole ratio for NAC derivatives and N-(2,4-dichlorobenzyl)chitosan (DS 0.52) for NBC derivatives. Their insecticidal and fungicidal activities were tested against larvae of the cotton leafworm Spodoptera littoralis (Boisduval) (Lepidoptera: Noctuidae), the grey mould Botrytis cinerea Pers (Leotiales: Sclerotiniaceae) and the rice leaf blast Pyricularia grisea Cavara (Teleomorph: Magnaporthe grisea (Hebert) Barr). The oral feeding bioassay indicated that all the derivatives had significant insecticidal activity at 5 g kg(-1) in artificial diet. The most active was N-(2-chloro-6-fluorobenzyl)chitosan, which caused 100% mortality at 0.625 g kg(-1), with an estimated LC50 of 0.32 g kg(-1). Treated larvae ceased feeding after 2-3 days; the mechanism of action remains unknown. In a radial hyphal growth bioassay with both plant pathogens, all derivatives showed a higher fungicidal action than chitosan. N-Dodecylchitosan, N-(p-isopropylbenzyl)chitosan and N-(2,6-dichlorobenzyl)chitosan were the most active against B cinerea, with EC50 values of 0.57, 0.57 and 0.52 g litre(-1), respectively. Against P grisea, N-(m-nitrobenzyl)chitosan was the most active, with 77% inhibition at 5 g litre(-1). The effect of different substitutions is discussed in relation to insecticidal and fungicidal activity.     

Strawberry Shelf Life,Composition, and Enzymes Activity in Response to Edible Chitosan Coatings

A series of active biodegradable coatings based on chitosan, gelatin, starch, and sorbitol with or without monoterpenes (geraniol and thymol) were prepared and applied on fresh strawberry fruit as postharvest treatments. The coated fruits were inoculated with fungal spores of Botrytis cinerea and stored for 7 days at 4 °C. Decay incidence, weight loss, anthocyanins, total soluble solids (TSS), total soluble phenolics (TSP), polygalacturonase (PGase), pectin-lyase (PLase), antioxidant activity, guaiacol peroxidase (G-POD), polyphenol oxidase (PPO), and catalase (CAT) were elucidated in the fruits of experimental sets and they were compared with that of controls. The coatings showed a significant effect on the development of quality variables, with the additional effect of geraniol and thymol as a function of the polysaccharide matrix. The coatings inhibited decay incidence, reduced weight loss, delayed changes in the contents of anthocyanin, TSS, and total soluble phenolics; inhibited the increase in G-POD and PPO activities; and retarded the reduction in CAT activity. Compared to the controls, all of the coatings had positive effects on the inhibition of cell wall degrading enzymes (PGase and PLase) and among all the tested coatings, T5, chitosan (1%) + starch (1%) + sorbitol (0.5%) + tween (0.05%) + thymol (0.02%) was the best. This formulation showed also the highest antimicrobial activity and the greatest effect on other physiochemical parameters and it can be suggested to use it as a useful coating agent for extending the shelf-life and maintaining quality of strawberry fruit.     

Clinical trial evaluating the efficacy and safety of cyclosporine in dogs with atopic dermatitis

OBJECTIVE: To determine efficacy and safety of cyclosporine in the treatment of atopic dermatitis among dogs in North America. DESIGN: Randomized controlled (phase 1) and open-label (phase 2) trials. ANIMALS: 268 dogs with atopic dermatitis. PROCEDURE: In phase 1, dogs were randomly assigned to be treated with cyclosporine (5 mg/kg [2.3 mg/Ib], PO, q 24 h) or a placebo. In phase 2, all dogs were treated with cyclosporine for 16 weeks. Frequency of cyclosporine administration was decreased if dogs improved clinically. RESULTS: At the end of phase 1, canine atopic dermatitis extent and severity index (CADESI) scores for dogs treated with cyclosporine were significantly lower than scores for control dogs. Percentage of dogs with severe pruritus decreased from 67% to 16% for the cyclosporine group but from 66% to only 61% for the control group. During phase 2, cyclosporine dosage was decreased to every-other-day administration in 39% of the dogs after 4 weeks. After 12 weeks, 22% of the dogs were treated twice weekly and 36% were treated every other day. After 16 weeks, CADESI score had decreased > 50% in 68% of the dogs and 47% of dogs had no or mild pruritus. The most frequent adverse reactions were gastrointestinal tract signs. CONCLUSIONS AND CLINICAL RELEVANCE: Results suggest that cyclosporine is efficacious for the treatment of atopic dermatitis in dogs and that frequency of cyclosporine administration can be reduced following an initial induction period. The drug was well tolerated.     

Differential effects of the endocrine-disrupting compounds bisphenol-A and octylphenol on gonadotropin secretion, in prepubertal ewe lambs

This study examined the effects of long-term exposure to the endocrine-disrupting compounds (EDCs) Bisphenol-A (BPA) and Octylphenol (OP) on gonadotrophin secretion in pre-pubertal female sheep. Four-week-old, female lambs were randomly allocated to four groups (n=6), and twice each week treated with i.m. injections of either corn oil (vehicle controls), diethylstilbestrol (DES; 0.175mg/kg), BPA (3.5mg/kg) or OP (3.5mg/kg). After 5 weeks of treatment, animals were ovariectomized (ovx) and ovary weights recorded. Two weeks later, blood samples were collected from lambs every 15min for 6h, for LH pulse analysis. Animals were then euthanased and adrenal and kidney weight recorded. An age-related increase in tonic LH secretion was noted in Control, BPA- and OP-treated lambs, but was absent in DES-treated lambs. Following ovx, LH secretion increased in all except DES-treated lambs; FSH concentrations increased in all groups. BPA and DES significantly suppressed LH pulse frequency (C: 6.7+/-0.3pulses/6h, DES: 1.5+/-0.8pulses/6h, BPA: 2.3+/-0.8pulses/6h) and amplitude (C: 7.1+/-1.0ng/ml, DES: 1.9+/-0.6ng/ml, BPA: 1.6+/-0.4ng/ml). OP had no effect on LH secretion (Frequency: 5.8+/-0.5pulses/6h, amplitude: 8.0+/-2.0ng/ml). Ovary weight was similar among all groups. Results show that chronic in vivo exposure of prepubertal female lambs to BPA, at levels lower than those reported previously, can have significant effects on LH secretion that are comparable to those seen following exposure to the known xenoestrogen, DES. Exposure to an equal dose of the EDC OP, over the equivalent period of time was without effect on gonadotropin secretion in the prepubertal ewe lamb. These results indicate that exposure of prepubertal female lambs to the EDC BPA can induce significant effects on gonadotropin secretion, the potential long-term effects of exposure and the effects of these changes on reproductive performance and efficacy, therefore, merit further study.     

No straight path: roaming in both ground- and excited-state photolytic channels of NO3 → NO + O2

Roaming mechanisms have recently been observed in several chemical reactions alongside trajectories that pass through a traditional transition state. Here, we demonstrate that the visible light-induced reaction NO(3) → NO + O(2) proceeds exclusively by roaming. High-level ab initio calculations predict specific NO Λ doublet propensities (orientations of the unpaired electron with respect to the molecular rotation plane) for this mechanism, which we discern experimentally by ion imaging. The data provide direct evidence for roaming pathways in two different electronic states, corresponding to both previously documented photolysis channels that produce NO + O(2). More broadly, the results raise intriguing questions about the overall prevalence of this unusual reaction mechanism.     

Response of Spring Phenology of Main Gymnosperm to Climate Change in Harbin City Proper

Global climate change has caused phenology change of vegetation.This is especially obvious in urban area.This paper reveals response mechanism of spring phenology of main gymnosperm in Harbin City proper to climate change based on relationship study between two typical phenophases(beginning of bud burst and beginning of leaf expansion) of Korean pine(Pinus koraiensis),Koyama spruce(Picea koraiensis Nakai),needle fir(Abies nephrolepis) and Pinus sylvestnis var.mongolica Litv.and the temperature of every ten ...     

Fire history of coniferous riparian forests in the Sierra Nevada

Fire is an important ecological process in many western U.S. coniferous forests, yet high fuel loads, rural home construction and other factors have encouraged the suppression of most wildfires. Using mechanical thinning and prescribed burning, land managers often try to reduce fuels in strategic areas with the highest fuel loads. Riparian forests, however, are often designated as areas where only limited management action can take place within a fixed-width zone. These highly productive forests have developed heavy fuel loads capable of supporting stand-replacing crown fires that can alter wildlife habitat and ecosystem function, and contribute to stream channel erosion. Objectives of this study were to determine whether adjacent coniferous riparian and upland forests burned historically with different frequencies and seasonalities, and whether these relationships varied by forest, site, and stream characteristics. We measured dendrochronological fire records in adjacent riparian and upland areas across a variety of forest, site and stream conditions at 36 sites in three sampling areas in the northern Sierra Nevada.