Chemical synthesis of 6-pentyl-2H-pyran-2-one: a natural antifungal biosynthesized by Trichoderma spp.

Trichoderma spp. biosynthesize 6-pentyl-2H-pyran-2-one (6-PP), a natural antifungal pyrone which could be used as biological control agent (BCA). Unfortunately, biotechnical processes are limited by inhibition of biomass at high concentration of 6-PP. We report herein a new easy synthesis of this natural pyrone, using readily available starting materials. This synthesis, compatible with a large production scale, permit to obtain overweight amounts of 6-PP that in biotechnological routes.     

Inhibition of cyclooxygenase-2 protects against cocaine hepatotoxicity in CF-1 mice

Gender differences in oral cocaine hepatotoxicity have been observed and lipopolysaccharide (LPS) was shown to potentiate cocaine hepatotoxicity in male CF-1 mice. Since cocaine and LPS inflict hepatocellular damage through the production of harmful reactive species, the role of cyclooxygenase-2 (COX-2) in gender-dependent cocaine hepatotoxicity was investigated. COX-2 increases nitric oxide (NO) synthesis and pro-inflammatory mediator production in response to hepatocellular insult. Male and female CF-1 mice were orally administered 20 mg kg^?1 cocaine hydrochloride once daily for 7 days. Four hours after the last cocaine administration, the mice received 12 × 10⁶ EU LPS intraperitoneally (cocaine + LPS). Mice receiving meloxicam (7.5 mg kg^?1, p.o.), a selective COX-2 inhibitor, were pretreated 1 h before each cocaine administration. Meloxicam prevented liver damage in males produced by cocaine and cocaine + LPS as evidenced by microscopic appearance and biochemical indices equivalent to saline treatment. Acetaminophen (APAP) was administered orally as a positive control which shows no gender dependency and elicited a hepatotoxic response in both males and females. Altered biochemical indices suggest that COX-2 is activated, possibly to a greater extent in females versus males in APAP-induced hepatotoxicity. Meloxicam prevented all oxidative stress changes induced in males following APAP. The results suggest that the induction of COX-2 is responsible, in part, for cocaine hepatotoxicity with and without LPS exposure in male mice.     

Aggregation pheromone ofCarpophilus freemani (Coleoptera: Nitidulidae): A blend of conjugated triene and tetraene hydrocarbons

Summary Males ofCarpophilus freemani Dobson (Coleoptera: Nitidulidae) produce an aggregation pheromone to which both sexes fly in a wind-tunnel bioassay. The major pheromone component (ca. 30 ng per male per day in volatile collections) was identified as (2E,4E,6E)-5-ethyl-3-methyl-2,4,6-nonatriene. A minor component, (2E,4E,6E,8E)-7-ethyl-3,5-dimethyl-2,4,6,8-undecatetraene, was 3–10% as abundant as the major triene and was 5–20% as active when compared at relative doses ranging from natural proportions to 1:1. These compounds act synergistically: a mixture of major and minor components in natural proportions attracted more than twice as many beetles as the major component alone, and the mixture fully accounted for the activity of male-derived volatile collections. Six other male-derived conjugated hydrocarbons, ranging from 2% down to 0.04% as abundant as the major component, were also identified. These are (in order of decreasing bioassay activity when compared on an equal-weight basis): (3E,5E,7E)-6-ethyl-4-methyl-3,5,7-decatriene, (2E,4E,6E)-5-ethyl-3-me-thyl-2,4,6-octatriene, (3E,5E,7E,9E)-8-ethyl-4,6-dimethyl-3, 5,7,9-dodecatetraene, (2E,4E,6E,8E)-3,5,7-trimethyl-2,4,6, 8-undecatetraene, (3E,5E,7E)-5-ethyl-7-methyl-3,5,7-undecatriene, and (2E,4E,6E)-3,5-dimethyl-2,4,6-nonatriene. All structure identifications were confirmed by synthesis. In the wind tunnel, the pheromone acted synergistically with host-type volatiles such as propyl acetate, valeric acid, and ethanol. This concept was verified by fields tests in California, in which there was dramatic synergism between the pheromone and fermenting host materials. Pheromone biosynthesis is discussed.     

How <Emphasis Type="Italic">Doratomyces stemonitis</Emphasis> copes with Benzoxazolin-2(3<Emphasis Type="Italic">H</Emphasis>)-one (BOA), its derivatives and detoxification products

Summary. Doratomyces stemonitis (Hyphomycetales, Dematiaceae) is a saprotrophic fungus belonging to the mycobiota of the cereal rhizosphere. The fungus is able to metabolize benzoxazolin-2-(3H)-one and a variety of its derivatives including higher plant detoxification products, microbial degradation products and the chemically rather stable 2-amino-(3H)-phenoxazin-3-one. D. stemonitis can use all of these compounds as sole C-sources but their utilization, especially that of microbial degradation products and 2-amino-(3H)-phenoxazin-3-one, seems to be highly energy consuming, resulting in slow mycelium growth and a change of colony morphology. Benzoxazolin-2-(3H)-one derived compounds induce the synthesis of different isoforms of a glycosylated protein with sequence homologies to the endo-1,3-β-glucanase Asp f2, an allergen from Aspergillus fumigatus and other Asp f2-like proteins e.g., from Verticillium dahliae or PRA1 antigen from Candida albicans. The induction of the protein is regarded as a stress response.     

Cationic dye adsorption onto natural and synthetic zeolites in the presence of Cs+ and Sr2+ ions

Adsorption of diazine dye safranine O (SO) in the presence of Cs⁺ and Sr²⁺ ions was investigated onto natural and synthetic zeolites in order to predict competition of cationic organic species with their radionuclides, which are the main fission products released into the environment. Adsorption of SO was measured up to the 40th day and the surface-diffusion coefficients (D_s) were estimated by applying Nernst–Planck approximation based on a homogeneous-surface-diffusion model. The values of D_s were 10 times higher on natural zeolite than those of synthesized zeolite from fly ash (FA) under hydrothermal conditions. Similarly, distribution coefficients (K_D) were considerably higher on the clinoptilolite-type natural zeolite. The zeolitized product of FA is mainly composed of analcime and sodalite. SO adsorption on natural zeolite was not influenced by Cs⁺ and Sr²⁺ ions, but it decreased at high concentrations on synthetic zeolite. The higher influence of the Sr²⁺ ions on SO⁺ adsorption showed that they compete with each other for the same adsorption sites. These results suggested that natural zeolite cannot be used for remediation of wastewater polluted with Cs and Sr radionuclides in the presence of organic cations, whilst FA zeolite has a potential for Sr removal.     

Copper (II) adsorption studies using models of synthetic humic acids

A polymer with characteristics similar to those of humic acids was obtained by synthesis reactions from oxidative polymerization in an alkaline medium using para-benzoquinone, hydroquinone and 4-aminobenzoic acid as precursors. Samples of natural and synthetic humic acid were used to examine the adsorption behavior of Cu²⁺ ions on these substrates. The mathematical models described by Langmuir and Freundlich equations were applied, yielding the maximum adsorption intensity values K′ (Langmuir), maximum adsorption capacity, b (Langmuir) and the adsorbent adsorption capacity, m (Freundlich). Based on solubility studies, pH 3 was selected for the development of the adsorption experiment. The Cu²⁺ ion presented a favorable adsorption, with RL (equilibrium parameter) responses in Langmuir isotherms falling within the desirable ranges.     

In vitro microbiological evaluation of novel 2-oxo-2H-chromene-3-carbaldehyde containing 1,3,4-thiadiazole moiety

4-(5-(Methylthio)-1,3,4-thiadiazol-2-ylamino)-2-oxo-2H-chromene-3-carbaldehyde (3) and 4-(5-(ethylthio)-1,3,4-thiadiazol-2-ylamino)-2-oxo-2H-chromene-3-carbaldehyde (4) were prepared. The structures of the newly synthesized compounds were characterized by infrared (IR), nuclear magnetic resonance (NMR) spectral data and elemental analysis. The synthesized compounds were screened in vitro for their antibacterial activities. The synthesized compounds demonstrated moderate antimicrobial activity.     

Royal jelly inhibited N-acetylation and metabolism of 2-aminofluorene in human liver tumor cells (J5)

The present study was carried out to evaluate the question of whether or not royal jelly affects N-acetylation and metabolism of 2-aminofluorene (2-AF) in the human liver tumor cell line (J 5). N-acetylation and metabolism of 2-AF in intact J5 cells was determined by using high performance liquid chromatography for the amounts of acetylated and nonacetylated 2-AF and profile of 2-AF metabolism. The results indicated that royal jelly displayed a dose-dependent inhibition of N-acetylation of 2-AF in J5 cells. Royal jelly also decreased the profile of 2-AF metabolites in J5 cells. This report is the first demonstration which showed that royal jelly affects N-acetylation of 2-AF in human liver tumor cells (J5).     

Multi-component synthesis and antimicrobial activity of novel imidazo[4,5-f] indol-7-yl)indolin-2-ones

A three-component one-pot protocol has been investigated for the synthesis of imidazo[4,5-f]indol-7-yl)indolin-2-ones from the commercially available materials. Structures of these compounds were established on the basis of IR, ¹H NMR, and mass spectral data. The title compounds were evaluated for their antimicrobial activity. Two compounds exhibited the potent antimicrobial activity.     

Microbiological evaluation of 4-(6-chloro-7H-purin-8-ylamino)-3-nitro-chromen-2-one with a comparison to antibacterial activity of standard drugs

Nucleophilic substitution of 4-chloro-3-nitro-2-oxo-2H-chromen-2-one 3 by 6-chloro-7H-purin-2-ylamine (a), yielded the corresponding 4-(6-chloro-7H-purin-8-ylamino)-3-nitro-chromen-2-one 4. The chemical structure of synthesized compound was characterized using IR and NMR spectra, and elemental analyses. The purified synthesized compound 4 was tested at concentrations 1, 3, 5 mg/ml for its antibacterial activity against three bacterial cultures: Staphylococcus aureus, Escherichia coli, and Bacillus cereus. The antibacterial activity of synthesized compound was compared to antibacterial activity of standard antibiotics cephalexine and streptomycin.     

Daily rhythm of O2-evolution in the cyanobacterium Trichodesmium thiebautii under natural and constant conditions

The rate of oxygen evolution by the tropical marine cyanobacterium Trichodesmium thiebautii was recorded at different times during the day in samples collected in 1992 from the Bahama Islands and the NE Caribbean Sea. This cyanobacterium is unique in that it is the only non-heterocystous diazotroph capable of N₂-fixation in daylight. Oxygen evolution was measured under conditions of natural day/night (LD, N=50), constant light (LL, N=14), and constant dark (DD, N=2×14). Photosynthesis vs intensity (P-I) relationships were calculated at various times of day, and the following parameters were used for further evaluation: photosynthesic capacity (P _max, 66 to 91 mg O₂ mg chl a ^-1 h^-1), initial slope of the P-I curve (, 0.23 to 0.27), dark respiration (R, 12 to 27 mg O₂ mg chl a ^-1 h^-1), and the intensity at which O₂ consumption is compensated by O₂ production (I _c, 78 to 160 Em^-2 s^-1). All means showed large standard deviations (for some parameters more than 200%). In some cases, these variations could be explained with a sinusoidal 24-h time course, but only the compensation point showed a significant daily variation (p0.001) in both LD and DD. The fact that the time course of I _c typical for natural conditions remains rhythmic under constant dark conditions strongly suggests a circadian regulation. Few circadian rhythms have been observed in prokaryotes, and this appears to be the first observation of such a rhythm in a cyanobacterium which fixes N₂ in daytime.     

In vitro and in vivo inhibition of Ca2+-Mg2+-ATPase activity by cadmium in post larvae of Penaeus monodon

Ca²⁺-Mg²⁺-ATPase is a membrane-bound enzyme and is responsible for regulating cytosolic free calcium. In vitro and in vivo effects of cadmium were studied on Ca²⁺-Mg²⁺-ATPase activity in plasma membrane/mitochondrial fraction of Penaeus monodon post larvae. In vitro studies revealed a concentration-dependent decrease in enzyme activity with an IC₅₀ value of 11.02?µM. In vivo experiments were conducted by exposing the post larvae to 1/10th (0.12?ppm) and 1/5th (0.24?ppm) of LC₅₀ values of cadmium for 30 days. Both ATPase activity and metal accumulation were estimated in post larvae exposed to 0.12 and 0.24?ppm of cadmium at different intervals of 24?h, 48?h, 96?h, 10 days and 30 days. ATPase activity showed a gradual decrease in post larvae on exposure to both the sub-lethal concentrations with respect to their controls and the decrease was significant (p?相似文献   

Mass spectral studies of 6‐n‐propyl‐2‐thiouracil,its oxygen,selenium and fluorinated congeners∗

The electron ionization mass spectra of the clinically used antithyroid agent 6‐n‐propyl‐2‐thiouracil (la), its minor metabolite, 6‐n‐propyluracil (lb) and their synthetic selenium and fluorinated analogs (1c and d) have been examined. The fragmentation pattern of these thiouracil and selenouracil studied bear strong similarities with those previously derived from a study of uracil analogs. Thus, the first step in the fragmentation is a retro Diel‐Alder decomposition with the loss of HCNX (X=O, S or Se) and the production of an ion radical which undergoes further fragmentation pathways which are discussed. 6‐n‐Propyl‐2‐selenouracil (1c) did show more complicated spectra due to the six natural isotopic abundance exhibited by the selenium atom. While the fluorinated analogs (1d) did substantiate the fact that the fragmentation pattern of these derivatives proceed through fragmentation between C₂ and N₃ bond since this produces the more resonance stabilized ion.     

Effect of Ca2+ on survival and development of metamorphosing bonefish (Albula sp.) leptocephali

Bonefish (Albula sp.) larvae (leptocephali) from the Gulf of California complete metamorphosis in ˜10 d in natural seawater (35‰S; Ca²⁺ conc = 10.5 mM). The increase in ossification that occurs near the end of the non-feeding metamorphic period, in addition to the ability of larvae to complete metamorphosis in dilute seawater (8‰ S) prompted the present study, where the effects of varying the external calcium ion concentration, [Ca²⁺]_e, of artificial seawater (ASW) on the survival, development and internal (whole-body) calcium ion content, (Ca²⁺)_i, of unfed metamorphosing larvae were investigated. Early-metamorphosing larvae placed in␣ASW, where [Ca²⁺]_e = 10.1 mM, survived for up to 10 d and developed normally without exogenous nutrients. In shorter-term experiments (4 to 5 d), no differences in survival were found for larvae in ASW with [Ca²⁺]_e rang-ing from 1.5 to 10.1 mM. However, in Ca²⁺-free ASW, most larvae died within 27 h and no larvae survived more than 42 h; the median lethal time (LT₅₀), and its 95% confidence limits, were 14.5 (10.0 to 20.9) h. High mortality (81% after 20 h) also occurred in 1.0 mM Ca²⁺ ASW, but 2 of 16 larvae tested survived for 96 h. The 96 h median tolerance limit (TL_M), corrected for control mortality, was 1.2 mM Ca²⁺. In natural seawater, larval (Ca²⁺)_i remained relatively constant ( = 0.419 mg larva⁻¹)␣in early- and intermediate-metamorphosing larvae, and then increased to a mean value of 0.739 mg larva⁻¹ in advanced larvae, indicating that Ca²⁺ was␣taken up from the medium at this stage; the increase in (Ca²⁺)_i corresponded to the period of ossification of the vertebral column. Internal (whole-body) magnesium ion content (Mg²⁺)_i showed no significant change during metamorphosis ( = 0.089 mg larva⁻¹). No significant differences in (Ca²⁺)_i were found in advanced larvae in natural seawater and those in ASW, with [Ca²⁺]_e ranging from 2.0 to 10.1 mM. However, clearing and staining revealed that ossification of the vertebral column had not yet occurred in advanced larvae from 2.0 to 10.1 mM Ca²⁺ ASW. Also, low [Ca²⁺]_e (1.0 to 2.0 mM) usually produced deformed larvae that swam erratically, at times showing “whirling” behavior. Received: 21 August 1996 / Accepted: 26 August 1996     

Chemical defense of a rare mint plant

Summary Analyses of leaf extracts ofDicerandra frutescens, a highly aromatic mint plant from central Florida listed as an endangered species, revealed presence of 12 closely related monoterpenes. The principal of these, (+)—trans-pulegol, is a new natural product, the synthesis of which is described. The terpenes are produced in glandular capsules that release their contents upon injury of the leaf. Data from bioassays with ants and cockroaches indicate that the terpenes serve for defense against insects.Dicerandra does, however, have a leaf-eating enemy, the caterpillar of a pyralid moth,Pyrausta panopealis. The discovery of a new natural product from an endangered species raises questions about the chemical implications of species extinction.     

H_2O_2致大鼠RTE细胞系氧化应激作用及GSH保护作用的体外研究

许多具有氧化作用的空气污染物,均能使细胞产生氧化损伤,使胸腺基质淋巴生成素(thymic stromal lymphopoietin,TSLP)含量上升。而TSLP是一种启动过敏性炎症的重要因子,会导致哮喘等疾病发生率的上升。在本研究中用过氧化氢(H_2O_2)模拟具有氧化作用的空气污染物进行染毒,研究细胞氧化应激水平的变化,并讨论还原型谷胱甘肽(GSH)对细胞受氧化损伤的保护作用。将大鼠支气管上皮细胞(RTE)分组培养,每组设置6个平行实验,分别用低、中、高剂量H_2O_2染毒3 h;高剂量设置1个重复,作为保护组,在染毒前用GSH保护2 h。结果显示,高剂量组H_2O_2(3.2 mmol·L~(~(-1)))染毒的细胞,其细胞活力下降(P0.01),丙二醛(MDA)水平上升(P0.01),TSLP水平上升(P0.05),与之相比,用GSH保护后的同剂量染毒组,上述指标得到全面缓解(P0.01)。这表明高浓度的H_2O_2会损伤细胞活力,并使MDA及TSLP水平上升,而GSH对TSLP及MDA的升高有极显著的抑制作用,即对细胞有一定的保护作用。     

Stereoisomeric composition of the sex pheromone of the pine sawfly <Emphasis Type="Italic">Microdiprion pallipes</Emphasis> (Hym., Diprionidae)

Summary. The basic chemical structure of the sex pheromone of the pine sawfly Microdiprion pallipes (Fallén) has earlier been identified as the propionate ester of (2S,3S,7R/S,11R/S)/(2R,3R,7R/S,11R/S)-3,7,11- trimethyl-2-tridecanol. We now report the results from further investigations on the male response to individual stereoisomers and to blends of stereoisomers, both in electroantennographic (EAG) recordings and in field trapping experiments. We also present our attempts to determine the stereochemistry of the compounds present in females of M. pallipes. By comparing gas chromatograms and mass spectra obtained from natural extracts with those from synthetic compounds it was found that the females contain one or more of the four (2S,3S,7R/S,11R/S)-3,7,11-trimethyl-2- tridecanol isomers (SS++-1). The active pheromone component is the corresponding propionate ester 2. In EAG experiments, males responded most strongly to five propionate ester samples, namely two four-isomer blends: SS++-2 and SR++-2, and three individual stereoisomers: SSSR-, SRRR- and SRSR-2. In a series of field trapping experiments it was found that males were attracted to the SR++-2 four-isomer blend and to the individual isomer SSSR-2. Based on the EAG-recordings and field responses of males and the stereoisomers found in the females, we suggest that the propionate ester of (2S,3S,7S,11R)-3,7,11-trimethyl-2- tridecanol (SSSR-2) is used as a main component of the sex pheromone in M. pallipes. Apparently the males react to other stereoisomers in addition to that or those produced by the females.     

Influence of light on algal symbionts of the deep water coral Leptoseris fragilis

Photoadaptations of zooxanthellae living within the deep water coral Leptoseris fragilis taken from the Gulf of Aqaba (Red Sea) were studied. Specimens-collected in summer 1988 between 110 and 120 m depth —were transplanted to 70 and 160 m. At each depth individuals were exposed in their natural growth position (oral side facing the surface) or in a reverse growth position (oral side facing the bottom). After 1 yr of exposure the corals were collected and the zooxanthellae were isolated. As a function of the availability of light with depth and growth position several algal parameters showed changes which are related to photoadaptations. The relatively low density of zooxanthellae of 0.15x10⁶ cellsxcm^-2 at a natural growth depth of 116 m decreased to 0.0034x10⁶ cellsxcm^-2 (2%) at 160 m in specimens growing with a natural orientation. In corals with a downward-facing oral surface at the same depth (160 m) only degenerated algae could be observed. With respect to depth dependence the volume of the algae decreased from 728 m³ at 116 m to 406 m³ at a depth of 160 m and the content of pigments increased. The augmentation of peridinin per cell was low (two times at 160 m compared to 116 m). Chlorophyll a and in particular chlorophyll c ₂ concentrations per cell were enhanced. Compared to natural amounts at 116 m, chl a was five times and chl c ₂ eight times higher at 160 m. At all depths the chl c ₂ content per cell was higher than for chl a. The formation of chl a/chl c ₂ complexes as light harvestor is discussed. Light harvesting, with chl c ₂ prevailing may be explained as a special type of chromatic adaptation of L. fragilis in a double sense: (1) in the habitat light short wavelengths predominate. This light can be directly absorbed with pigments such as chl a and chl c ₂. (2) Host pigments absorb visible violet light and transform these wavelengths, less suitable for photosynthesis, into longer ones by means of autofluorescence. The emitted longer wavelengths fit the absorption maxima of the algal pigments. Thus the host supports photosynthesis of his symbionts. Corals exposed at 160 m depth with a downward facing oral surface were alive after 1 yr and the host wavelength transforming pigment system was still present, but zooxanthellae were absent or degenerated. The light field at 160 m seems therefore to be critical: the combined photoadaptations of host and symbionts, allowing photosynthesis under barren light conditions, seem to be exhausted. In L. fragilis the photoadaptive strategies of host and symbionts cooperate harmoniously. In addition, the adaptations are interlocked with the particular light situation of the habitat with respect to light quantity and quality. The cooperation of physical and organismic parameters examplifies how evolution and, in particular, coevolution has led to optimal fitness.     

Carbon and nitrogen dynamics during growth and degradation of phytoplankton under natural surface irradiance

Under conditions of natural irradiance, the development and decline of a flagellate-dominated phytoplankton population was followed in a coastal North Atlantic pond over a 3 d period in summer 1986. Irradiance negatively affected phytoplankton biomass estimated as chlorophyll a, which decreased during the day at photosynthetically available radiation (PAR) levels above 600 to 1000 mol m^-2s^-1; chlorophyll a increased at PAR values below this threshold. In addition, an inverse relationship was found between changes in chlorophyll a and changes in dissolved inorganic nitrogen, indicating synthesis of nitrogenous biomass mainly at night and degradation mainly during the day, with intense exchanges of material between the particulate and dissolved nitrogen fractions. The natural abundance of ¹³C in particulate matter increased initially, and then remained constant, and was controlled mainly by the ratio -carboxylases activity: ribulose biphosphate carboxylase activity. The hypothesis that the latter enzyme is broken down under high irradiance and is partly responsible for increases in external dissolved nitrogen was rejected.     

Identification and biological activity of sex pheromone components from females of the plum moth Illiberis rotundata Jordan (Lepidoptera: Zygaenidae: Procridinae)

The plum moth, Illiberis rotundata Jordan (Lepidoptera: Zygaenidae: Procridinae), is a pest of orchards in Japan and China. Few chemical ecological studies have been directed towards the Zygaenidae and particularly the Procridinae. To investigate the sex pheromone of this species, extracts of pheromone glands from adult female I. rotundata were analyzed by coupled gas chromatography-electroantennography (GC-EAG) and coupled gas chromatography-mass spectrometry (GC-MS). Whilst GC-EAG on male moths showed an active peak, identified as 2-butyl (7Z)-dodecenoate, GC-MS also revealed the presence of the homologue 2-butyl (9Z)-tetradecenoate. Electroantennographic investigations, as well as field tests, strongly suggested the natural compounds to have the (R)-configuration at the stereogenic centre. Field results demonstrate 0.2 mg of a 1:1-mixture of (2R)-butyl (7Z)-dodecenoate and (2R)-butyl (9Z)-tetradecenoate to be a powerful lure that may be used in pest control measures against I. rotundata. The chemical structures of the new pheromone components show the same features as those of other zygaenid species: unsaturated fatty acids esterified with a short chain chiral alcohol. This is the first example of a two-component blend constituting the pheromone of a procridinid species.