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.     

Identification,pathogenicity and community dynamics of fungi and oomycetes associated with pea root rot in northern France

The pea root rot complex is a major concern for green pea production worldwide. This study aimed at characterizing its composition and dynamics throughout a cropping season in northern France. To this end, fungi and oomycetes were isolated from green pea plant roots with symptoms sampled at the flowering stage in 22 fields in 2017, and at the pea emergence, elongation and flowering stages in two fields in 2018. Out of 646 isolates collected, 317 were identified using molecular markers. Fusarium oxysporum, F. solani and F. redolens were highly predominant. Pathogenicity tests separated the isolates into four aggressiveness groups. F. solani isolates were the most aggressive. Phylogenetic analysis of their TEF1 sequences showed that they mainly belonged to the F. pisi lineage, and that F. oxysporum isolates were genetically close to isolates from the UK that did not belong to the forma specialis pisi. In addition, several Clonostachys rhizophaga isolates are reported for the first time to cause pea root rot. The oomycetes were rarely found and were represented by a few Pythium spp. isolates. Lastly, this study shows that the fungal and oomycete communities associated with pea root rot change during the cropping season. The level of dissimilarity of the root-rot-associated communities decreased throughout the cropping season towards a more similar composition at the flowering stage, dominated by F. solani, F. oxysporum and F. redolens. The proportion of nonpathogenic to weakly pathogenic isolates decreased progressively during the growing season in favour of moderately to highly pathogenic isolates.     

Expression of β2-integrin on monocytes and blood polymorphonuclear leukocytes in the periparturient period in dairy cows

The hypothesis that an altered expression of CD11/CD18 on bovine circulating monocytes, polymorphonuclear leukocytes (PMN), or both, contributes to an increased mastitis susceptibility in periparturient cows was tested. Expression of CD18 and CD11a, -b, -c on bovine monocytes and PMN were assessed in 8 Friesian-Holstein cows by flow cytometry from 2 wk before calving to 5 wk after calving. Minor changes in adhesion molecule expression levels were detected throughout the experimental period. Compared with PMN, monocytes exhibited an expression level that was similar for CD18, higher for CD11a and CD11c, but lower for CD11b. Differences in density may reflect the relative importance of these adhesion molecules on both leukocyte types. In this study, the decreased number of milk resident macrophages and PMN observed during the periparturient period could not be attributed to changes of CD11/CD18 levels on circulating leukocytes.     

Quantitative determination of sulfur-containing wine odorants at sub parts per billion levels. 2. Development and application of a stable isotope dilution assay

[(2)H(10)]-4-Mercapto-4-methylpentan-2-one (d(10)-1), [(2)H(2)]-3-mercaptohexan-1-ol (d(2)-2), and [(2)H(5)]-3-mercaptohex-1-yl acetate (d(5)-3), deuterated analogues of impact odorants of wines, were used to determine quantitatively the natural compounds in white wines (Muscadet, Sauvignon, and Bacchus) with a stable isotope dilution assay using gas chromatography coupled either with ion trap tandem mass spectrometry (GC-ITMS-MS) or with atomic emission detection monitored on sulfur-selective acquisition (GC-AED). The thiol compounds were recovered from wines by liquid-liquid extraction, then purified from the wine extracts by covalent chromatography, and analyzed. The quantitative determination of 4-mercapto-4-methylpentan-2-one 1 in the wines that were analyzed was performed better with GC-AED than with GC-ITMS-MS under the conditions that were used. However, the detection limit of the method was higher than the odor threshold of 4-mercapto-4-methylpentan-2-one 1 in wine (5 vs 0.8 ng/L). The levels of this compound in the Sauvignon and Bacchus wines were much higher than its odor threshold, but it was not detectable in the Muscadet wines. On the contrary, GC-ITMS-MS was much more sensitive than GC-AED for detection of 3-mercaptohexan-1-ol 2 and 3-mercaptohex-1-yl acetate 3, and the detection limits were much lower than their odor thresholds in wine. The former compound was detected in all of the Muscadet wines that were analyzed at levels always higher than its odor detection threshold, while the latter occurred at levels higher than its odor threshold in only one Muscadet wine.     

Designing responsive buckled surfaces by halftone gel lithography

Self-actuating materials capable of transforming between three-dimensional shapes have applications in areas as diverse as biomedicine, robotics, and tunable micro-optics. We introduce a method of photopatterning polymer films that yields temperature-responsive gel sheets that can transform between a flat state and a prescribed three-dimensional shape. Our approach is based on poly(N-isopropylacrylamide) copolymers containing pendent benzophenone units that allow cross-linking to be tuned by irradiation dose. We describe a simple method of halftone gel lithography using only two photomasks, wherein highly cross-linked dots embedded in a lightly cross-linked matrix provide access to nearly continuous, and fully two-dimensional, patterns of swelling. This method is used to fabricate surfaces with constant Gaussian curvature (spherical caps, saddles, and cones) or zero mean curvature (Enneper's surfaces), as well as more complex and nearly closed shapes.     

Constraints on light interception efficiency due to shoot architecture in broad-leaved Nothofagus species

Shoot architecture may significantly alter mean quantum flux on foliage and thus, photosynthetic productivity. There is currently only limited information about plastic alterations in shoot structure caused by within-canopy variation in mean integrated irradiance (Q(int)) in broad-leaved trees. We studied leaf and shoot structure, and nitrogen and carbon content in late-successional, widely distributed, temperate, broad-leaved Nothofagus taxa to determine the architectural controls on light harvesting and photosynthetic performance. Nothofagus fusca (Hook. f.) Oersted has larger leaves and less densely leaved shoots than the N. solandri varieties. Nothofagus solandri var. solandri (Hook. f.) Oersted is characterized by rounder leaves that potentially have a larger overlap than the ovate-triangular leaves of N. solandri var. cliffortioides (Hook. f.) Poole. Leaf dry mass (M(A)) and nitrogen content (N(A)) per unit area increased with increasing Q(int) in all species, demonstrating enhanced investment of photosynthetic biomass in high light. Although M(A) differed between species at a common irradiance, there was a uniform relationship between N(A) and Q(int) across species. Leaf carbon content per dry mass and leaf dry mass to fresh mass ratio also scaled positively with irradiance, suggesting greater structural investments in high light. In all species, shoots became more horizontal and flatter at lower Q(int), implying an enhanced use efficiency of direct irradiance in natural leaf positions. In contrast, irradiance effects on leaf aggregation varied among species. Across the data, leaf overlap or leaf area density was often greater at lower irradiances, possibly as a result of limited carbon availability for shoot axis extension growth. In N. fusca, leaves of which were more aggregated in high light, the shoot silhouette to total leaf area ratio (S(S)) declined strongly with increasing irradiance, demonstrating a lower light harvesting efficiency at high Q(int). This effect was only moderate in N. solandri var. cliffortioides and S(S) was independent of Q(int) in N. solandri var. solandri. Although the efficiency of light interception at high irradiances was lowest in N. fusca, this species had the greatest nitrogen content per unit shoot silhouette area (2N(A)/S(S)), indicating superior shoot-level photosynthetic potential. These data collectively demonstrate that shoot architecture significantly affects light interception and photosynthesis in broad-leaved trees, and that structural carbon limitations may constrain leaf light harvesting efficiency at low irradiance.     

Simulating in situ ammonia volatilization losses in the North China Plain using a dynamic soil‐crop model

Ammonia (NH₃) volatilization is an important N loss pathway in intensive agriculture of the North China Plain (NCP). Simulation models can help to assess complex N and water processes of agricultural soil–crop systems. Four variations (Var) of a sub‐module for the deterministic, process‐based HERMES model were implemented ranging from simple empirical functions (Var 3 and 4) to process‐oriented approaches (Var 1 and 2) including the main processes of NH₃ volatilization, urea hydrolysis, nitrification from ammonium‐based N fertilizer, and changes in soil solution pH. Ammonia volatilization, plant growth, and changes in ammonium and nitrate pools in the soil over several winter wheat–summer maize double‐crop rotations at three locations in the NCP were simulated. Results were calibrated with two data sets (Dongbeiwang 1, Shunyi) and validated using two data sets (Dongbeiwang 2, Quzhou). They showed that the ammonia volatilization sub‐module of the HERMES model worked well under the climatic and soil conditions of N China. Although the simpler equations, Var 3 and 4, showed lower deviations to observed volatilization across all sites and treatments with a mean absolute error (MAE) of 1.8 and 1.4 in % of applied N, respectively, compared to process‐oriented approaches, Var 1 and 2, with a MAE of 2.2 and 1.9 in % of applied N, respectively. Environmental conditions were reflected better by the process‐oriented approaches. Generally, simulation results were satisfying but simulated changes in topsoil pH need further verification with measurements.     

Long-term organic phosphorus mineralization in Spodosols under forests and its relation to carbon and nitrogen mineralization

In forest soils where a large fraction of total phosphorus (P) is in organic forms, soil micro-organisms play a major role in the P cycle and plant availability since they mediate organic P transformations. However, the correct assessment of organic P mineralization is usually a challenging task because mineralized P is rapidly sorbed and most mineralization fluxes are very weak. The objectives of the present work were to quantify in five forest Spodosols at soil depths of 0-15 cm net mineralization of total organic P and the resulting increase in plant available inorganic P and to verify whether net or gross P mineralization could be estimated using the C or N mineralization rates. Net mineralization of total organic P was derived from the net changes in microbial P and gross mineralization of P in dead soil organic matter. We studied very low P-sorbing soils enabling us to use lower extractants to assess the change in total inorganic P as a result of gross mineralization of P in dead soil organic matter. In addition, to enable detection of gross mineralization of P in dead soil organic matter, a long-term incubation (517 days) experiment was carried out. At the beginning of the experiment, total P contents of the soils were very low (19-51 μg g⁻¹) and were essentially present as organic P (17-44 μg g⁻¹, 85-91%) or microbial P (6-14 μg g⁻¹; 24-39%). Conversely, the initial contents of inorganic P were low (2-7 μg g⁻¹; 9-15%). The net changes in the pool size of microbial P during the 517 days of incubation (4-8 μg g⁻¹) and the amounts of P resulting from gross mineralization of dead soil organic matter (0.001-0.018 μg g⁻¹ day⁻¹; 0.4-9.5 μg g⁻¹ for the entire incubation period) were considerable compared to the initial amounts of organic P and also when compared to the initial diffusive iP fraction (<0.3 μg g⁻¹). Diffusive iP corresponds to the phosphate ions that can be transferred from the solid constituents to the soil solution under a gradient of concentration. Net mineralization of organic P induced an important increase in iP in soil solution (0.6-10 μg g⁻¹; 600-5000% increase) and lower increases in diffusive iP fractions (0.3-5 μg g⁻¹; 300-2000% increase), soil solid constituents having an extremely low reactivity relative to iP. Therefore, soil micro-organisms and organic P transformations play a major role in the bioavailability of P in these forest soils. In our study, the dead soil organic matter was defined as a recalcitrant organic fraction. Probably because gross mineralization of P from this recalcitrant organic fraction was mainly driven by the micro-organisms’ needs for energy, the rates of gross mineralization of C, N and P in the recalcitrant organic fraction were similar. Indirect estimation of gross mineralization of P in dead soil organic matter using the gross C mineralization rate seems thus an alternative method for the studied soils. However, additional studies are needed to verify this alternative method in other soils. No relationships were found between microbial P release and microbial C and N releases.     

Desiccation and product accumulation constrain heterotrophic anaerobic respiration in peats of an ombrotrophic temperate bog

To gain insight into the effects of drying and rewetting events on anaerobic respiration in ombrotrophic peat soils, we investigated bacterial sulfate (SO₄) reduction and methane (CH₄) production in anaerobic incubations of intact peat microcores from 30 to 40 cm depth of Mer Bleue bog, Ontario/Canada. Concentrations of dissolved SO₄, carbon dioxide (CO₂), CH₄, acetate, and hydrogen (H₂) were recorded and net turnover rates calculated from regression. Gross rates of bacterial sulfate reduction were determined by ³⁵SO₄ tracer incubation. After incubation, the peat was dried and rewetted, with saturated peat serving as control. CO₂ production was initially rapid (up to <360 nmol cm^?3 d^?1) and slowed towards an endpoint of 2–3 mmol l^?1, which was only partly related to thresholds of Gibbs free energies of the involved processes. Acetate rapidly accumulated to levels of 600–800 μmol l^?1 and remained constant thereafter. CH₄ production (0–2.8 nmol cm^?3 d^?1) was small and delayed, even after SO₄ was depleted, by about 30–40 d. Hydrogenotrophic methanogenesis was endergonic and the process thus likely followed an acetotrophic pathway. Drying and rewetting replenished the SO₄ pool, enhanced SO₄ reduction rates and suppressed methanogenesis. The overall contribution of net SO₄ reduction and methanogenesis to the CO₂ production rate was small (0.5–22%) and only enhanced in replicates subjected to drying (35–62%). The major fraction of respiration in the incubated peat cores thus followed yet unidentified pathways.