Stimulation of ethylene evolution and abscission in cotton by 2-chloroethanephosphonic Acid

Ethrel, a mixture of 2-chloroethanephosphonic acid and its ethyl ester, hastens abscission of leaves, debladed petioles, and flower buds of cotton plants (Gossypium hirsutum, L.). Both young and old leaves abscissed while still green. Application of Ethrel stimulated evolution of ethylene, and this response preceded abscission. Air concentrations of ethylene around enclosed, treated-plants were adequate to produce abscission in plants. Non-treated plants defoliated when enclosed with plants sprayed with Ethrel. The stimulation of abscission of explant petioles by Ethrel was reversed by naphthalene acetic acid. The stimulation of abscission by Ethrel was concluded to be mediated by ethylene.     

Auxin-like activity of 1,2-benzisothiazole derivatives

The 1,2-benzisothiazol-3-yl-acetic and -3-yl-butyric acids and their ethyl esters, amides and nitriles are generally active in the split pea stem test, induce an increase in both length and fresh weight of pea internodes, inhibit the development of pea roots, and, with some exceptions (1,2-benzisothiazol-3-yl-butyric amide and nitrile), induce the production of ethylene by pea segments. Moreover they stimulate cell multiplication and raise the degree of hydration of Helianthus tuberosus explants grown in vitro. These activities are often similar or sometimes higher than those of IAA. By contrast, the 1,2-benzisothiazole derivatives having a side chain with an odd number of carbon atoms (-3-yl-carboxylic and propionic acids, amides, ethyl esters and nitriles) are inactive or show a far lower activity.     

Biological evaluation of newly synthesized aryl(thio)carbamoyl derivatives of 1- and 1-(2-aminoethyl)-piperazines

Twelve 1-methyl and acetyl-4-substituted piperazines, evaluated as potential herbicides and plant growth regulators, were synthesized by condensation of 1-methyl-piperazine and 1-[2-(acetylamino)ethyl]-4-acetyl-piperazine with the corresponding aryliso(thio)cyanates. These piperazines, which incorporate a piperazine ring and aryl(thio)carbamoyl groups connected directly or through an ethylene group, are new chemical families of herbicides and cytokinin mimics. Structure–activity relationships for the screened compounds were evaluated and discussed. The greatest herbicidal activity against Triticum aestivum was observed with compounds that contained the three structural elements: piperazine ring, ethylene group and 4-fluorophenylcarbamoyl group. Compounds having a combination of two active moieties–piperazine ring and 4-halogenophenylthiocarbamoyl group, also showed high herbicidal activity against T. aestivum. The compound, in which the un-substituted phenylcarbamoyl group was directly connected to the piperazine ring, showed cytokinin-like activity and significantly stimulated betacyanin synthesis in Amaranthus caudatus.     

Gravitropism in Higher Plant Shoots : IV. Further Studies on Participation of Ethylene

Ethylene at 1.0 and 10.0 cubic centimeters per cubic meter decreased the rate of gravitropic bending in stems of cocklebur (Xanthium strumarium L.) and tomato (Lycopersicon esculentum Mill), but 0.1 cubic centimeter per cubic meter ethylene had little effect. Treating cocklebur plants with 1.0 millimolar aminoethoxyvinylglycine (AVG) (ethylene synthesis inhibitor) delayed stem bending compared with controls, but adding 0.1 cubic centimeter per cubic meter ethylene in the surrounding atmosphere (or applying 0.1% ethephon solution) partially restored the rate of bending of AVG-treated plants. Ethylene increases in bending stems, and AVG inhibits this. Virtually all newly synthesized ethylene appeared in bottom halves of horizontal stems, where ethylene concentrations were as much as 100 times those in upright stems or in top halves of horizontal stems. This was especially true when horizontal stems were physically restrained from bending. Ethylene might promote cell elongation in bottom tissues of a horizontal stem or indicate other factors there (e.g. a large amount of `functioning' auxin). Or top and bottom tissues may become differentially sensitive to ethylene. Auxin applied to one side of a vertical stem caused extreme bending away from that side; gibberellic acid, kinetin, and abscisic acid were without effect. Acidic ethephon solutions applied to one side of young seedlings of cocklebur, tomato, sunflower (Helianthus annuus L.), and soybean (Glycine max [L.] Merr.) caused bending away from that side, but neutral ethephon solutions did not cause bending. Buffered or unbuffered acid (HCl) caused similar bending. Neutral ethephon solutions produced typical ethylene symptoms (i.e. epinasty, inhibition of stem elongation). HCl or acidic ethephon applied to the top of horizontal stems caused downward bending, but these substances applied to the bottom of such stems inhibited growth and upward bending—an unexpected result.     

Immobilization of penicillin acylase on acrylic carriers

Penicillin acylase obtained from E. Coli (E. C. 3.5.1.11) was covalently bound via glutaric aldehyde to acrylic carriers crosslinked with divinylbenzene or ethylene glycol dimethacrylate. The best enzymatic preparation was obtained by using ethyl acrylate/ ethylene glycol dimethacrylate copolymer. 1 cm³ of the carrier bound 6.4 mg of protein, having 72% activity in relation to the native enzyme. The preparation lost only 10% of its initial activity after 100 d of storage at 4°C. A negligible effect of immobilization on the enzyme activity at different temperatures or pH as well as significant increase of the stability of the immobilized enzyme at elevated temperatures were observed.Abbreviations BA butyl acrylate - AE ethyl acrylate - PA penicillin acylase - 6-APA 6-aminopenicillanic acid - EGDMA ethylene glycol dimethacrylate - DVB divinylbenzene     

Understanding the role of the trifluoromethyl group in reactivity and regioselectivity in [3+2] cycloaddition reactions of enol acetates with nitrones. A DFT study

The mechanism of the [3+2] cycloaddition (32CA) reaction of C-phenyl-N-methylnitrone with ethyl trifluoroacetoacetate has been theoretically studied at the MPWB1K/6-311G(d,p) level. This 32CA reaction, in which the enol form of the β-keto ester participates as the ethylene component, takes place with complete ortho regioselectivity and exo stereoselectivity. The presence of the CF₃ group in the β-position in the enol acetate accelerates the 32CA reaction, but it does not modify the regioselectivity, which is controlled by the presence of the ester group. While ortho regioselectivity is reproduced by the MPWB1K calculations, the endo selectivity is not. The inclusion of solvent effects slightly decreases the reactivity but does not modify the gas phase selectivities. Analysis of the DFT global reactivity indices and the Parr functions in reagents provide a rationalization for the participation of ethyl trifluoroacetoacetate and the regioselectivity in this zw-type 32CA reaction.     

Changes in ester compounds and higher alcohols of awamori during aging

The total contents of ethyl acetate, ethyl caproate, ethyl caprylate, isoamyl caproate, ethyl caprate, isoamyl caprylate, ethyl laurate, isoamyl caprate, ethyl myristate, ethyl palmitate, ethyl stearate, ethyl oleate, ethyl linoleate and β-phenethyl acetate in awamori ranged from 70.67 to 569.72 mg per l a t 100 per cent alcohol. The ratio of ethyl acetate content to the total content of 14 ester compounds (ethyl acetate/total esters) ranged from 0.59 to 0.86, and that of ethyl caprylate to the total esters was from 0.98 ×10⁻² to 8.26 × 10⁻². Ethyl acetate was the main component of ester compounds followed in descending order by ethyl caprate, ethyl palmitate and ethyl caprylate. Of the higher alcohols, awamori contained only β-phenethyl alcohol in significant quantity.On aging in kame 13 of 16 ester compounds tended to decrease distinctly and the remaining 3 components to show no distinct change, while 3 of 5 higher alcohols tended to increase distinctly. On aging in non-porous containers, however, 3 of 16 ester compounds decreased distinctly, and 3 of 5 higher alcohols increased distinctly. In the process of aging, esters underwent hydrolysis in kame but not in non-porous containers.     

Activity and stability of Escherichia coli β-galactosidase in cosolvent systems

The kinetic parameters of E.coli -galactosidase were not altered by the addition of 2-propanol or ethyl acetate (1.6% v/v). While ethylene glycol (1.6% v/v) doubled the values of both KM (0.29 mM) and kcat (1393 s–), tetraethyleneglycol-dimethylether (Tetraglyme,1.6% v/v) preserved KM, but decreased kcat. At 50°C all the cosolvents dramatically shortened the enzymatic half life, and so did Tetraglyme and 2-propanol at 28°C. At 28°C, both ethyl acetate and ethylene glycol stabilised the enzyme 9- and 6-fold respectively. This fact, together with the activation effect of ethylene glycol may lead to practical applications. © Rapid Science Ltd. 1998     

Modifying action of gamma-radiation in mutagenesis of E. coli WU36-10 induced by ethylene oxide, ethyl methanesulfonate and methyl methanesulfonate

The influence of gamma-radiation pre-exposure on ethylene oxide, ethyl methanesulfonate and methyl methanesulfonate mutagenesis in Escherichia coli WU36-10 was studied. Pretreatment with gamma-radiation resulted, in the case of subsequent treatment with ethylene oxide and ethyl methanesulfonate, in a decrease of the frequency of leu+ revertants, and in the case of subsequent treatment with methyl methanesulfonate, in an increase of this mutation frequency.     

The structure of an enzyme–product complex reveals the critical role of a terminal hydroxide nucleophile in the bacterial phosphotriesterase mechanism

A detailed understanding of the catalytic mechanism of enzymes is an important step toward improving their activity for use in biotechnology. In this paper, crystal soaking experiments and X-ray crystallography were used to analyse the mechanism of the Agrobacterium radiobacter phosphotriesterase, OpdA, an enzyme capable of detoxifying a broad range of organophosphate pesticides. The structures of OpdA complexed with ethylene glycol and the product of dimethoate hydrolysis, dimethyl thiophosphate, provide new details of the catalytic mechanism. These structures suggest that the attacking nucleophile is a terminally bound hydroxide, consistent with the catalytic mechanism of other binuclear metallophosphoesterases. In addition, a crystal structure with the potential substrate trimethyl phosphate bound non-productively demonstrates the importance of the active site cavity in orienting the substrate into an approximation of the transition state.     

Promotion by Ethylene of the Capability to Convert 1-Aminocyclopropane-1-carboxylic Acid to Ethylene in Preclimacteric Tomato and Cantaloupe Fruits

The intact fruits of preclimacteric tomato (Lycopersicon esculentum Mill) or cantaloupe (Cucumis melo L.) produced very little ethylene and had low capability of converting 1-aminocyclopropane-1-carboxylic acid (ACC) to ethylene. When these unripe tomato or cantaloupe fruits were treated with ethylene for 16 hours there was no increase in ACC content or in ethylene production rate, but the tissue's capability to convert ACC to ethylene increased markedly. Such an effect was also observed in fruits of tomato mutants rin and nor, which do not undergo ripening and the climacteric increase in ethylene production during the senescence. The development of this ethylene-forming capability induced by ethylene increased with increasing ethylene concentration (from 0.1 to 100 microliters per liter) and duration (1 to 24 hours); when ethylene was removed this capability remained high for sometime (more than 24 hours). Norbornadiene, a competitive inhibitor of ethylene action, effectively eliminated the promotive effect of ethylene in tomato fruit. These data indicate that the development of the capability to convert ACC to ethylene in preclimacteric tomato and cantaloupe fruits are sensitive to ethylene treatment and that when these fruits are exposed to exogenous ethylene, the increase in ethylene-forming enzyme precedes the increase in ACC synthase.     

Stereospecific conversion of 1-aminocyclopropanecarboxylic Acid to ethylene by plant tissues : conversion of stereoisomers of 1-amino-2-ethylcyclopropanecarboxylic Acid to 1-butene

Inasmuch as the molecule of 1-aminocyclopropanecarboxylic acid (ACC) possesses reflective symmetry but lacks rotational symmetry, the two chemically alike methylene groups can be distinguished by a stereospecific enzyme. To determine whether ACC conversion to ethylene by plant tissues proceeds in a stereospecific fashion, the four stereoisomers of 1-amino-2-ethylcyclopropanecarboxylic acid (AEC) were administered to postclimacteric apple (Malus sylvestris Mill., var. Golden Delicious), excised preclimacteric cantaloupe (Cucumis melo L., var. reticulatis Naud cv. PMR-45), and etiolated mung bean (Vigna radiata L., Wilczek, var. Berken) hypocotyls. In each case (1R,2S)-AEC was the preferred substrate yielding 1-butene. In contrast, all AEC isomers were converted equally well to butene by chemical oxidation using NaOCl. Both ACC and AEC appear to be substrates for the same enzyme since both reactions are inhibited in parallel by N₂ or Co²⁺, both reactions are induced in parallel by excision, and when both substrates are present simultaneously each will act as an inhibitor with respect to the other. The aforementioned observations indicate that ACC is stereospecifically converted to ethylene. For AEC to be the most active precursor of 1-butene, the ethyl substituent should be trans to the carboxyl group and the pro-(S) methylene group should be unsubstituted. This observation leads to the suggestion that the enzyme interacts with amino, carboxyl, and pro-(S) methylene groups, a configuration corresponding to a l-amino acid. This view is consistent with the observation that the l-forms of alanine and methionine inhibit the conversion of ACC to ethylene more than the corresponding d-amino acids in the mung bean hypocotyl system.     

Ethanol reduces sensitivity to ethylene and delays petal senescence in cut Tweedia caerulea flowers

Tweedia caerulea flowers are sensitive to ethylene and the closing of the flowers, a characteristic of senescence, is accelerated by exposure to ethylene. T. caerulea flowers were continuously treated with ethanol at concentrations of 0, 2, 4, 6, 8, 10 or 12 %, and treatment levels at 4 % and above showed delayed closing. Ethanol accelerated climacteric increase in ethylene production from flowers. Although ethylene production was higher in gynoecium than in petals, ethanol treatment accelerated ethylene production by both organs. Exposure to ethylene increased autocatalytic ethylene production, and production was further accelerated by ethanol treatment. When flowers treated with ethanol were exposed to ethylene, senescence was delayed compared to that for untreated flowers, suggesting that ethanol reduces the sensitivity of flowers to ethylene. These results indicate that treatment with ethanol delays petal senescence in cut T. caerulea flowers, possibly through reduced sensitivity to ethylene.     

Suppression of ethylene levels promotes morphogenesis in pepper (Capsicum annuum L.)

Ethylene and polyamines (PAs) are two phytohormones that play important roles during in vitro morphogenesis of several plant species. The interaction between ethylene and PAs has been of interest because both have S-adenosylmethionine as a precursor. To study the influence of ethylene and PAs on in vitro morphogenesis of an ornamental pepper, we added an ethylene scavenger, PAs, a PA inhibitor, and compounds that affect ethylene biosynthesis and activity to the regeneration medium. Regeneration frequencies increased in response to treatment with ethylene inhibitors (aminoethoxyvinylglycine and silver thiosulfate) and an ethylene scavenger (mercury perchlorate). Treatment with the ethylene precursor 1-aminocyclopropane-1-carboxylic acid reduced the regeneration frequency, increased callus formation, and increased ethylene levels; similar results were obtained in response to treatment with the PA inhibitor methylglyoxal-bis(guanylhydrazone). By contrast, treatment with PAs (particularly spermidine and spermine) decreased ethylene levels, increased the regeneration frequency, and increased shoot bud formation. These results suggest a coordinated regulation of ethylene and polyamines because the suppression of ethylene levels using ethylene inhibitors, polyamines, or mercury perchlorate increased the in vitro regeneration frequency and morphogenic responses of Capsicum annuum L.     

Ethylene antagonizes the inhibition of germination in Arabidopsis induced by salinity by modulating the concentration of hydrogen peroxide

The capacity of plants to achieve successful germination and early seedling establishment under high salinity is crucial for tolerance of plants to salt. The gaseous hormone ethylene has been implicated in modulating salt tolerance, but the detailed role of how ethylene modulates the response of early seedling establishment to salt is unclear. To better understand the role of the ethylene signal transduction pathway during germination and seedling establishment, an ethylene insensitive mutation (ein2-5) and an ethylene sensitive mutation (ctr1-1) of Arabidopsis were analyzed under saline conditions and compared with the wild type plant (Col-0) as control. High salinity (>100?mM NaCl) inhibited and delayed germination. These effects were more severe in the ethylene insensitive mutants (ein2-5) and less severe in the constitutive ethylene sensitive plants (ctr1-1) compared with Col-0 plants. Addition of the ethylene precursor 1-aminocyclopropane-1-carboxylic acid (ACC) or inhibitors of ethylene action implied that ethylene was essential for early seedling establishment under normal and saline conditions. Salt stress increased the endogenous concentration of hydrogen peroxide (H₂O₂) in germinating seeds and ACC reduced its concentration. Our results suggest that ethylene promotes germination under salinity by modulating the endogenous concentration of H₂O₂ in germinating seeds. These findings demonstrate that ethylene is involved in regulating germination as an initiator of the process rather than consequence, and that ethylene promotes germination by modulating the endogenous concentration of H₂O₂ in germinating seeds under salinity.     

Regulation of Auxin-induced Ethylene Production in Mung Bean Hypocotyls: Role of 1-Aminocyclopropane-1-Carboxylic Acid

Ethylene production in mung bean hypocotyls was greatly increased by treatment with 1-aminocyclopropane-1-carboxylic acid (ACC), which was utilized as the ethylene precursor. Unlike auxin-stimulated ethylene production, ACC-dependent ethylene production was not inhibited by aminoethoxyvinylglycine, which is known to inhibit the conversion of S-adenosylmethionine to ACC. While the conversion of methionine to ethylene requires induction by auxin, the conversion of methionine to S-adenosylmethionine and the conversion of ACC to ethylene do not. It is proposed that the conversion of S-adenosylmethionine to ACC is the rate-limiting step in the biosynthesis of ethylene, and that auxin stimulates ethylene production by inducing the synthesis of the enzyme involved in this reaction.