Antiparasitic activity of prenylated benzoic acid derivatives from Piper species

Fractionation of dichloromethane extracts from the leaves of Piper heterophyllum and P. aduncum afforded three prenylated hydroxybenzoic acids, 3-[(2E,6E,10E)-11-carboxy-3,7,15-trimethyl-2,6,10,14-hexadecatetraenyl)-4,5-dihydroxybenzoic acid, 3-[(2E,6E,10E)-11-carboxy-13-hydroxy-3,7,15-trimethyl-2,6,10,14-hexadecatetraenyl]-4,5-dihydroxybenzoic acid and 3-[(2E,6E,10E)-11-carboxy-14-hydroxy-3,7,15-trimethyl-2,6,10,15-hexadecatetraenyl]-4,5-dihydroxybenzoic acid, along with the known compounds, 4,5-dihydroxy-3-(E,E,E-11-formyl-3,7,15-trimethyl-hexadeca-2,6,10,14-tetraenyl)benzoic acid (arieianal), 3,4-dihydroxy-5-(E,E,E-3,7,11,15-tetramethyl-hexadeca-2,6,10,14-tetraenyl)benzoic acid, 4-hydroxy-3-(E,E,E-3,7,11,15-tetramethyl-hexadeca-2,6,10,14-tetraenyl)benzoic acid, 3-(3,7-dimethyl-2,6-octadienyl)-4-methoxy-benzoic acid, 4-hydroxy-3-(3,7-dimethyl-2,6-octadienyl)benzoic acid and 4-hydroxy-3-(3-methyl-1-oxo-2-butenyl)-5-(3-methyl-2-butenyl)benzoic acid. Their structures were elucidated on the basis of spectroscopic data, including homo- and heteronuclear correlation NMR experiments (COSY, HSQC and HMBC) and comparison with data reported in the literature. Riguera ester reactions and optical rotation measurements established the compounds as racemates. The antiparasitic activity of the compounds were tested against three strains of Leishmania spp., Trypanosoma cruzi and Plasmodium falciparum. The results showed that 3-(3,7-dimethyl-2,6-octadienyl)-4-methoxy-benzoic acid exhibited potent and selective activity against L. braziliensis (IC₅₀ 6.5 μg/ml), higher that pentamidine used as control. Moreover, 3-[(2E,6E,10E)-11-carboxy-3,7,15-trimethyl- 2,6,10,14-hexadecatetraenyl)-4,5-dihydroxybenzoic acid and 4-hydroxy-3-(3-methyl-1-oxo-2-butenyl)-5-(3-methyl-2-butenyl)benzoic acid showed moderate antiplasmodial (IC₅₀ 3.2 μg/ml) and trypanocidal (16.5 μg/ml) activities, respectively.     

Acylated cyanidin 3-sambubioside-5-glucosides from the purple-violet flowers of Matthiola longipetala subsp. bicornis (Sm) P. W. Ball. (Brassicaceae)

A novel acylated cyanidin 3-sambubioside-5-glucoside was isolated from the purple-violet flowers of Matthiola longipetala subsp. bicornis (Sm) P. W. Ball. (family: Brassicaceae), and determined to be cyanidin 3-O-[2-O-(2-O-(trans-feruloyl)-β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] by chemical and spectroscopic methods. In addition, two known acylated cyanidin 3-sambubioside-5-glucosides, cyanidin 3-O-[2-O-(2-O-(trans-sinapoyl)-β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] and cyanidin 3-O-[2-O-(β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] were identified in the flowers.     

Cytokinin activity of N-phenyl-N′-(4-pyridyl)urea derivatives

We have synthesized 35 N-phenyl-N′-(4-pyridyl)urea derivatives and tested their cytokinin activity in the tobacco callus bioassay. Among them, N-phenyl-N′- (2-chloro-4-pyridyl)urea is highly active, the optimum concentration of which is lower than 4 × 10^?9 M (0.001 ppm), 3 compounds, i.e. N-(2-methylphenyl)-N′-(2-chloro-4-pyridyl)urea, N-(3-methylphenyl)-N′-(2-chloro-4-pyridyl)urea and N-(3-chlorophenyl)-N′-(2-chloro-4-pyridyl) urea are as active as N⁶-benzyladenine (concentration for optimum yield: 4.4 × 10^?8 M or 0.01 ppm), and N-phenyl-N′-(2-methyl-4-pyridyl)urea and N-(2-chlorophenyl)-N′-(2-chloro-4-pyridyl)urea are as active as N-phenyl-N′-(4-pyridyl)urea (concentration for optimum yield: 4.7 × 10^?7 M or 0.1 ppm), while the activity of the other 29 compounds are not so remarkable and 11 of them are almost or completely inactive.     

Cooperative aspects of hydrogen bonding in carbohydrates

Various compounds related to the antibacterial, sulfanilamide drugs have been prepared from dehydro-l-ascorbic acid or its d-erythro analog by reaction with hydrazines related to sulfanilamide, sulfadiazine, sulfamerazine, sulfamethazine, and sulfamethoxydiazine, whereby the 2-mono- and 2,3-bis-(hydrazone) were isolated. After opening of the lactone ring in the bis(hydrazones) with alkali, nucleophilic attack, on the carbonyl group, of the imino nitrogen atom of the 3-hydrazone residue afforded 3-(l-threo-glycerol-1-yl)-1-phenyl- and -1-(p-sulfamylphenyl)-4,5-pyrazole-dione 4-(p-sulfamylphenlhydrazone) and the related 3-(d-erythro-glycerol-1-yl)compounds. Whereas acetylation of l-threo-2,3-hexodiulosono-1,4-lactone 2,3-bis(p-sulfamylphenylhydrazone) (9) and 3-(l-threo-glycerol-1-yl)-1-(p-sulfamylphenyl)-4,5-pyrazoledione 4-(p-sulfamylphenylhydrazone) (15) gave the O-acetyl derivatives, benzoylation of 15 gave the di-N-benzoy ltri-O-benzoyl compound. Reaction of 9 with cupric chloride gave 3,6-anhydro-3-(p-suIfamylphenylazo) -l-xylo-2-hexulosono-1,4-lactone 2-(p-sulfamylphenylhydrazone). The 3-(l-threo-glycerol-1-yl)-1-(p-sulfamylphenyl)flavazole (35) was prepared by the rearrangement of 3-[(1-p-sulfamylphenyl)hydrazono-l-threo-trihydroxybutyl]-2-quinoxalinont (33). Periodate oxidation of 15,33, and 35 gave 3-formyl-1-(p-sulfamylphenyl)-4,5-pyrazoledione 4-(p-sulfamylphenylhydrazone), 3-1-[(p-sulfamylphenyl)hydrazono]glyoxal-1-yl]-2-quinoxalinone, and 3-formyl-1-(p-sulfamylphenyl)flavazole, respectively. The i.r. and n.m.r. spectral data for some of these derivatives are reported.     

Acid-catalyzed transformation of 13(S)-hydroperoxylinoleic acid into epoxyhydroxyoctadecenoic and trihydroxyoctadecenoic acids

Acid treatment of (13S)-(9Z,11E)-13-hydroperoxy-9,11-octadecadienoic acid in tetrahydrofuran-water solvent afforded mainly (11R,12R,13S)-(Z)-12,13-epoxy-11-hydroxy-9-octadecenoic acid, diastereomeric (Z)-11,12,13-trihydroxy-9-octadecenoic acids and four isomers of (E)-9,12,13(9,10,13)-trihydroxy-10(11)-octadecenoic acid. Other minor products were oxooctadecadienoic, (E)-9(13)-hydroxy-13(9)-oxo-10(11)-octadecenoic and (E)-12-oxo-10-dodecenoic acids. A heterolytic mechanism for acid catalysis was indicated, even though most of the products characterized also have been observed as a result of homolytic decomposition of the hydroperoxide via an oxy radical. Most of the products found in this study have been observed as metabolites of (13S)-(9Z,11E)-13-hydroperoxy-9,11-octadecadenoic acid in biological systems, and analogous compounds have been reported as metabolites of (12S)-(5Z,8Z,10E, 14Z)-12-hydroperoxy-5,8,10,14-hydroperoxy-5,8,10,14-eicosatetraenoic acid in either blood platelets or lung tissue.     

N-Acetyldopamine derivatives from Periostracum Cicadae

Five new N-acetyldopamine (NADA) derivatives (1–5) and one known NADA quinone methide (6) were isolated from Periostracum Cicadae (the cast-off shell of the cicada Cryptotympana pustulata Fabricius), which is known as chantui in China and is used in traditional Chinese medicine to treat soreness of the throat, hoarseness, itching, and spasms. By combined analysis of one-dimensional and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, CD spectra, and chemical evidence, the structures of the isolated compounds were established as (R)-N-(2-(3,4-dihydroxyphenyl)-1-ethoxy-2-oxoethyl)acetamide (1), (1R,2R)-N-(1,2-diethoxy-2-(3,4-dihydroxyphenyl)-ethyl)acetamide (2), (R)-N-(1-acetamido-2-ethoxy-2-(3,4-dihydroxyphenyl)-ethyl)acetamide (3), (1R,2R)-N-(2-(3,4-dihydroxyphenyl)-2-ethoxy-1-methoxyethyl)acetamide (4), (1S,2S)-N-(2-(3,4-dihydroxyphenyl)-2-ethoxy-1-methoxyethyl)acetamide (5), and (R)-N-(2-(3,4-dihydroxyphenyl)-2-methoxyethyl)acetamide (6).     

Interaction specificity of Arabidopsis 14-3-3 proteins with phototropin receptor kinases

Phototropin receptor kinases play an important role in optimising plant growth in response to blue light. Much is known regarding their photochemical reactivity, yet little progress has been made to identify downstream signalling components. Here, we isolated several interacting proteins for Arabidopsis phototropin 1 (phot1) by yeast two-hybrid screening. These include members of the NPH3/RPT2 (NRL) protein family, proteins associated with vesicle trafficking, and the 14-3-3 lambda (λ) isoform from Arabidopsis. 14-3-3λ and phot1 were found to colocalise and interact in vivo. Moreover, 14-3-3 binding to phot1 was limited to non-epsilon 14-3-3 isoforms and was dependent on key sites of receptor autophosphorylation. No 14-3-3 binding was detected for Arabidopsis phot2, suggesting that 14-3-3 proteins are specific to phot1 signalling.

Structured summary

MINT-7146953: PHOT1 (uniprotkb:O48963) physically interacts (MI:0915) with ARF7 (uniprotkb:Q9LFJ7) by two hybrid (MI:0018)MINT-7147335: PHOT1 (uniprotkb:O48963) physically interacts (MI:0914) with 14-3-3 phi (uniprotkb:P46077) by far Western blotting (MI:0047)MINT-7146854: PHOT1 (uniprotkb:O48963) physically interacts (MI:0915) with RPT2 (uniprotkb:Q682S0) by two hybrid (MI:0018)MINT-7147215: PHOT1 (uniprotkb:O48963) physically interacts (MI:0914) with 14-3-3 lambda (uniprotkb:P48349) by anti tag coimmunoprecipitation (MI:0007)MINT-7147044, MINT-7147185, MINT-7147200, MINT-7147413: PHOT1 (uniprotkb:O48963) physically interacts (MI:0914) with 14-3-3 lambda (uniprotkb:P48349) by far Western blotting (MI:0047)MINT-7146983: PHOT1 (uniprotkb:O48963) physically interacts (MI:0915) with 14-3-3 lambda (uniprotkb:P48349) by two hybrid (MI:0018)MINT-7146871: PHOT1 (uniprotkb:O48963) physically interacts (MI:0915) with NPH3-like (uniprotkb:Q9S9Q9) by two hybrid (MI:0018)MINT-7146905: PHOT1 (uniprotkb:O48963) physically interacts (MI:0915) with ARF2 (uniprotkb:Q9M1P5) by two hybrid (MI:0018)MINT-7147364: PHOT1 (uniprotkb:O48963) physically interacts (MI:0914) with 14-3-3 upsilon (uniprotkb:P42645) by far Western blotting (MI:0047)MINT-7147234: PHOT1 (uniprotkb:O48963) physically interacts (MI:0914) with 14-3-3 kappa (uniprotkb:P48348) by far Western blotting (MI:0047)     

Synthesis of carbon-11-labeled 5-HT6R antagonists as new candidate PET radioligands for imaging of Alzheimer’s disease

Carbon-11-labeled serotonin (5-hydroxytryptamine) 6 receptor (5-HT₆R) antagonists, 1-[(2-bromophenyl)sulfonyl]-5-[¹¹C]methoxy-3-[(4-methyl-1-piperazinyl)methyl]-1H-indole (O-[¹¹C]2a) and 1-[(2-bromophenyl)sulfonyl]-5-methoxy-3-[(4-[¹¹C]methyl-1-piperazinyl)methyl]-1H-indole (N-[¹¹C]2a), 5-[¹¹C]methoxy-3-((4-methylpiperazin-1-yl)methyl)-1-(phenylsulfonyl)-1H-indole (O-[¹¹C]2b) and 5-methoxy-3-((4-[¹¹C]methylpiperazin-1-yl)methyl)-1-(phenylsulfonyl)-1H-indole (N-[¹¹C]2b), 1-((4-isopropylphenyl)sulfonyl)-5-[¹¹C]methoxy-3-((4-methylpiperazin-1-yl)methyl)-1H-indole (O-[¹¹C]2c) and 1-((4-isopropylphenyl)sulfonyl)-5-methoxy-3-((4-[¹¹C]methylpiperazin-1-yl)methyl)-1H-indole (N-[¹¹C]2c), 1-((4-fluorophenyl)sulfonyl)-5-[¹¹C]methoxy-3-((4-methylpiperazin-1-yl)methyl)-1H-indole (O-[¹¹C]2d) and 1-((4-fluorophenyl)sulfonyl)-5-methoxy-3-((4-[¹¹C]methylpiperazin-1-yl)methyl)-1H-indole (N-[¹¹C]2d), were prepared from their O- or N-desmethylated precursors with [¹¹C]CH₃OTf through O- or N-[¹¹C]methylation and isolated by HPLC combined with SPE in 40–50% radiochemical yield, based on [¹¹C]CO₂ and decay corrected to end of bombardment (EOB). The radiochemical purity was >99%, and the molar activity (MA) at EOB was 370–740?GBq/μmol with a total synthesis time of ～40-min from EOB.     

Neolignans from an Aniba species

The trunk wood of an Amazonian Aniba (Lauraceae) species contains, besides dillapiol and the benzodioxane-type neolignan eusiderin, four bicyclo(3.2.1)octanoid neolignans. These comprise representatives of the canellin-type: the known methoxycanellin-A and the novel compounds characterized as (1R, 3S, 4S, 5S, 6S, 7R)-1-allyl-4-hydroxy-3, 5-dimethoxy-7-methyl-6-(3′-methoxy-4′, 5′-methylenedioxyphenyl)-8-oxo-bicyclo(3.2.1)octane; (1R, 3S, 4S, 5S, 6S, 7R)-1-allyl-4-hydroxy-3, 5-dimethoxy-7-methyl-6-(3′, 4′, 5′-trimethoxyphenyl)-8-oxobicyclo(3.2.1)octane and (1R, 4R, 5R, 6S, 7R, 8S)-1-allyl-4, 8-dihydroxy-5-methoxy-7-methyl-6-(3′-methoxy-4′,5′-methylenedioxyphenyl)-3-oxobicyclo(3.2.1)octane.     

N-Substituted acetamide glycosides from the stems of Ephedra sinica

Five new N-mono-/bis-substituted acetamide glycosides, N-{4-O-[3-O-(4-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (1), N-methyl-N-{4-O-[3-O-(4-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (2), N-methyl-N-{4-O-[3-O-(6-O-benzoyl-4-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (3), N-methyl-N-{4-O-[3-O-(6-O-benzoyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (4), and N-methyl-N-{4-O-[3-O-(6-O-trans-cinnamoyl-4-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (5), along with one known acetamide derivative, N-methyl-N-(4-hydroxyphenethyl)-acetamide, the shared aglycone of 2–5, were isolated from the ethanol extract of the stems of Ephedra sinica. The structures of these new compounds were elucidated on the basis of extensive spectroscopic examination, mainly including multiple 1D and 2D NMR and HRESIMS examinations, and qualitative chemical tests. All N,N-bissubstituted acetamide glycosides were found to show the obvious rotamerism, as in the case of the isolated known N-methyl-N-(4-hydroxyphenethyl)-acetamide, under the experimental NMR conditions, with the ratios of integrated intensities between anti- and syn-rotamers always being found to be about 4 to 3.     

Anthocyanins with unusual furanose sugar (apiose) from leaves of Synadeniumgrantii (Euphorbiaceae)

Four anthocyanins, cyanidin 3-O-(2″-(5?-(E-p-coumaroyl)-β-apiofuranosyl)-β-xylopyranoside)-5-O-β-glucopyranoside, cyanidin 3-O-(2″-(5?-(E-p-coumaroyl)-β-apiofuranosyl)-β-xylopyranoside), cyanidin 3-O-(2″-(5?-(E-caffeoyl)-β-apiofuranosyl)-β-xylopyranoside) and cyanidin 3-O-(2″-(5?-(E-feroyl)-β-apiofuranosyl)-β-xylopyranoside) were isolated from leaves of African milk bush, (Synadeniumgrantii Hook, Euphorbiaceae) together with the known cyanidin 3-O-β-xylopyranoside-5-O-β-glucopyranoside and cyanidin 3-O-β-xyloside. The four former pigments are the first reported anthocyanins containing the monosaccharide apiose, and the three 5?-cinnamoyl derivative-2″-(β-apiosyl)-β-xyloside subunits have previously not been reported for any compound.     

Synthesis of new 1-(4-methane(amino)sulfonylphenyl)-5-(4-substituted-aminomethylphenyl)-3-trifluoromethyl-1H-pyrazoles: A search for novel nitric oxide donor anti-inflammatory agents

A group of 1-(4-methane(amino)sulfonylphenyl)-5-(4-substituted-aminomethylphenyl)-3-trifluoromethyl-1H-pyrazoles (12a–f) was synthesized and evaluated as anti-inflammatory agents. While all the compounds (20 mg/kg) showed significant anti-inflammatory activity after 3 h of inflammation induction (69–89%) as compared to celecoxib (80%), 1-(4-methanesulfonylphenyl)-5-(4-methylaminomethylphenyl)-3-trifluoromethyl-1H-pyrazole (12a) was found to be the most effective one (89%). The synthesis of model hybrid nitric oxide donor N-diazen-1-ium-1,2-diolate derivatives of 1-(4-methanesulfonylphenyl)-5-(4-substituted-aminomethylphenyl)-3-trifluoromethyl-1H-pyrazoles (10a–f) requires further investigation since the reaction of N-(4-(1-(4-(methylsulfonyl)phenyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl)benzyl)ethanamine (12b) or 1-(4-(1-(4-(methylsulfonyl)phenyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl)benzyl)piperazine (12c) with nitric oxide furnished N-nitroso derivatives (13 and 14), respectively, rather than the desired N-diazen-1-ium-1,2-diolate derivatives (10b and 10c).     

Evidence for leptin receptor isoforms heteromerization at the cell surface

Leptin mediates its metabolic effects through several leptin receptor (LEP-R) isoforms. In humans, long (LEPRb) and short (LEPRa,c,d) isoforms are generated by alternative splicing. Most of leptin’s effects are believed to be mediated by the OB-Rb isoform. However, the role of short LEPR isoforms and the possible existence of heteromers between different isoforms are poorly understood. Using BRET1 and optimized co-immunoprecipitation, we observed LEPRa/b and LEPRb/c heteromers located at the plasma membrane and stabilized by leptin. Given the widespread coexpression of LEPRa and LEPRb, our results suggest that LEPRa/b heteromers may represent a major receptor species in most tissues.

Structured summary

MINT-7714817: LEPRb (uniprotkb:P48357-1) physically interacts (MI:0915) with LEPRb (uniprotkb:P48357-1) by anti tag co-immunoprecipitation (MI:0007)MINT-7714785: LEPRc (uniprotkb:P48357-2) physically interacts (MI:0915) with LEPRc (uniprotkb:P48357-2) by bioluminescence resonance energy transfer (MI:0012)MINT-7714951, MINT-7714744: LEPRa (uniprotkb:P48357-3) physically interacts (MI:0915) with LEPRa (uniprotkb:P48357-3) by bioluminescence resonance energy transfer (MI:0012)MINT-7714859: LEPRb (uniprotkb:P48357-1) physically interacts (MI:0915) with LEPRa (uniprotkb:P48357-3) by anti tag co-immunoprecipitation (MI:0007)MINT-7714885, MINT-7714672: LEPRb (uniprotkb:P48357-1) physically interacts (MI:0915) with LEPRb (uniprotkb:P48357-1) by bioluminescence resonance energy transfer (MI:0012)MINT-7714835: LEPRa (uniprotkb:P48357-3) physically interacts (MI:0915) with LEPRa (uniprotkb:P48357-3) by anti tag co-immunoprecipitation (MI:0007)MINT-7714914, MINT-7714723, MINT-7714759: LeprB (uniprotkb:P48357-1) physically interacts (MI:0915) with LEPRa (uniprotkb:P48357-3) by bioluminescence resonance energy transfer (MI:0012)MINT-7714703, MINT-7714936, MINT-7714772: LEPRb (uniprotkb:P48357-1) physically interacts (MI:0915) with LEPRc (uniprotkb:P48357-2) by bioluminescence resonance energy transfer (MI:0012)MINT-7714872: LEPRb (uniprotkb:P48357-1) physically interacts (MI:0915) with LEPRc (uniprotkb:P48357-2) by anti tag co-immunoprecipitation (MI:0007)     

Isolation and synthesis of trans- and cis-(−)-clovamides and their deoxy analogues from the bark of Dalbergia melanoxylon

N-(3′,4′-Dihydroxy-trans-cinnamoyl)-3-(3,4-dihydroxyphenyl)-L-alanine [(?)-clovamide], the major phenolic metabolite (0.1%) in the bark of Dalbergia melanoxylon, is associated with minor proportions of its cis-isomer, and similar pairs of geometrical isomers of their deoxy analogues N-(4′-hydroxycinnamoyl)-3-(3,4-dihydroxyphenyl)-L-alanine and N-(4′-hydroxycinnamoyl)-3-(4-hydroxyphenyl)-L-alanine. (?)-Trans-clovamide is synthesized by direct condensation of the acid chloride of caffeic acid with L-DOPA. Diagnostic CD spectra of these compounds and ¹³C spectra of (?)-trans- and (?)-cis-clovamides are recorded.     

Diarylheptanoids from Curcuma comosa

Three new diarylheptanoids, designated 1-(3,4-dihydroxyphenyl)-7-(4-hydroxyphenyl)-(6E)-6-hepten-3-ol (1), 1-(3-hydroxyphenyl)-7-(3,4-dihydroxyphenyl)-3-methoxy-(6E)-6-heptene (2), (3R, 5R)-1-(3,4-dihydroxyphenyl)-7-phenyl-heptane-3,5-diol (3) and three known compounds, were isolated from rhizomes of Curcuma comosa. Structures of the compounds were determined by spectroscopic data analysis.     

Facile radiosynthesis of new carbon-11-labeled propanamide derivatives as selective androgen receptor modulator (SARM) radioligands for prostate cancer imaging

The androgen receptor (AR) is an attractive target for the treatment and molecular imaging of prostate cancer. New carbon-11-labeled propanamide derivatives were first designed and synthesized as selective androgen receptor modulator (SARM) radioligands for prostate cancer imaging using the biomedical imaging technique positron emission tomography (PET). The target tracers, (S)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-[¹¹C]methoxyphenoxy)-2-methylpropanamide ([¹¹C]8a), (S)-2-hydroxy-3-(2-[¹¹C]methoxyphenoxy)-2-methyl-N-(4-nitro-3-(trifluoromethyl)phenyl)propanamide ([¹¹C]8e), (S)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(4-[¹¹C]methoxyphenoxy)-2-methylpropanamide ([¹¹C]8c) and (S)-2-hydroxy-3-(4-[¹¹C]methoxyphenoxy)-2-methyl-N-(4-nitro-3-(trifluoromethyl)phenyl)propanamide ([¹¹C]8g), were prepared by O-[¹¹C]methylation of their corresponding precursors, (S)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-hydroxyphenoxy)-2-methylpropanamide (9a), (S)-2-hydroxy-3-(2-hydroxyphenoxy)-2-methyl-N-(4-nitro-3-(trifluoromethyl)phenyl)propanamide (9b), (S)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(4-hydroxyphenoxy)-2-methylpropanamide (9c) and (S)-2-hydroxy-3-(4-hydroxyphenoxy)-2-methyl-N-(4-nitro-3-(trifluoromethyl)phenyl)propanamide (9d), with [¹¹C]CH₃OTf under basic conditions and isolated by a simplified C-18 solid-phase extraction (SPE) method in 55 ± 5% (n = 5) radiochemical yields based on [¹¹C]CO₂ and decay corrected to end of bombardment (EOB). The overall synthesis time from EOB was 23 min, the radiochemical purity was >99%, and the specific activity at end of synthesis (EOS) was 277.5 ± 92.5 GBq/μmol (n = 5).     

Sulphated polysaccharides of the grateloupiaceae family : Part VII. Investigation of the acetolysis products of a partially desulphated sample of the polysaccharide of pachymenia carnosa

Investigation of the acetolysis products of a partially desulphated sample of the polysaccharide isolated from Pachymenia carnosa led to the isolation and characterization of the following oligosaccharides: 3-O-α-D-galactopyranosyl-D-galactose (1), 4-O-β-D-galactopyranosyl-D-galactose (2), 3-O-(2-O-methyl-α-D-galactopyranosyl)-D-galactose (3), a 4-O-galactopyranosyl-2-O-methylgalactose (4), 3-O-α-D-galactopyranosyl-6-O-methyl-D-galactose (5), 4-O-β-D-galactopyranosyl-2-O-methyl-D-galactose (6), 2-O-methyl-4-O-(6-O-methyl-β-D-galactopyranosyl)-D-galactose (14), O-β-D-galactopyranosyl-(1→4)-O-α-D-galactopyranosyl-(1→3)-D-galactose (8), O-α-D-galactopyranosyl-(1→3)-O-β-D-galactopyranosyl-(1→4)-D-galactose (9), O-β-D-galactopyranosyl-(1→4)-O-α-(2-O-methyl-D-galactopyranosyl)-(1→3)-D-galactose (11), O-α-(2-O-methyl-D-galactopyranosyl)-(1→3)-O-β-D-galactopyranosyl-(1→4)-D-galactose (12), O-α-D-galactopyranosyl-(1→3)-O-β-D-galactopyranosyl-(1→4)-2-O-methyl-D-galactose (13), O-α-(2-O-methyl-D-galactopyranosyl)-(1→3)-O-β-D-galactopyranosyl-(1→4)-2-O-methyl-D-galactose (16), and O-β-D-galactopyranosyl-(1→4)-O-α-D-galactopyranosyl-(1→3)-O-β-D-galactopyranosyl-(1→4)-D-galactose (10). In addition, evidence was obtained for the presence of 4-O-(6-O-methyl-β-D-galactopyranosyl)-D-galactose (7) and O-β-D-galactopyranosyl-(1→4)-O-α-D-galactopyranosyl-(1→3)-6-O-methyl-D-galactose (15).     

Synthesis of C-glycopyranosylfuran derivatives by reaction of dialdehydes with cyanoacetamide

The reaction of diglycol- and thiodiglycol-aldehyde (1a,b) with cyanoacetamide yields cis-3,5-diacetoxy-4-carbamoyl-4-cyano-tetrahydropyran (2a) and -tetrahydrothiopyran (2b). When this reaction is applied to (2S)-2-(3-ethoxycarbonyl-2-methyl-5-furyl)-3,5-dihydroxy-1,4-dioxane (1c), (2S)-3,5-dihydroxy-2-(3-methoxycarbonyl-2-methyl-5-furyl)-1,4-dioxane (1d), and (2S,3R,5S)-2-(3-acetyl-2-methyl-5-furyl)-3,5-dihydroxy-1,4-dioxane (1e), 5-(3-carbamoyl-3-cyano-3-deoxy-β-d-xylo-pentopyranosyl)-3-ethoxycarbonyl-2-methylfuran (2c), 5-(2,4-di-O-acetyl-3-carbamoyl-3-cyano-3-deoxy-β-d-xylo-pentopyranosyl)-3-methoxycarbonyl-2-methylfuran (2e), and 3-acetyl-5-(2,4-di-O-acetyl-3-carbamoyl-3-cyano-3-deoxy-β-d-xylo-pentopyranosyl)-2-methylfuran (2f), respectively, are formed with (4S,5S)-4-carbamoyl-4-cyano-2-(3-ethoxycarbonyl-2-methyl-5-furyl)-5-hydroxy-5,6-dihydropyran (3a) and (4S,5S)-4-carbamoyl-4-cyano-5-hydroxy-2-(3-methoxycarbonyl-2-methyl-5-furyl)-5,6-dihydropyran (3b) as minor products. The dehydration of 2a,b, 5-(2,4-di-O-acetyl-3-carbamoyl-3-cyano-3-deoxy-β-d-xylo-pentopyranosyl)-3-ethoxycarbonyl-2-methylfuran (2d), 2e, and 2f yields cis-3,5-diacetoxy-4,4-dicyano-tetrahydropyran and -tetrahydrothiopyran (2l,m), and the 5-(2,4-di-O-acetyl-3,3-dicyano-3-deoxy-β-d-erythro-pentopyranosyl) derivatives (2n–p) of 3-ethoxycarbonyl-2-methylfuran, 3-methoxycarbonyl-2-methylfuran, and 3-acetyl-2-methylfuran, respectively.     

The attachment of poly(ribitol phosphate) to lipoteichoic acid carrier

2-Acetamido-3,4,6-tri-O-acetyl-1-N-[N-(benzyloxycarbonyl)-L-aspart-1-oyl-(L-leucyl-L-threonyl-N²-tosyl-L-lysine p-nitrobenzyl ester)-4-oyl]-2-deoxy-β-D-glucopyranosylamine (21) and 2-acetamido-3,4,6-tri-O-acetyl-1-N-[N-(benzyloxycarbonyl)-L-aspart-1-oyl-(L-leucyl-L-threonyl-N²-tosyl-L-lysine p-nitrobenzyl ester)-4-oyl]-2-deoxy-β-D-glucopyranosylamine (22), 2-acetamido-3,4,6-tri-O-acetyl-1-N-[N-(benzyloxycarbonyl)-L-aspart-1-oyl-(glycine ethyl ester)-4-oyl]-2-deoxy-β-D-glucopyranosylamine, and 2-acetamido-3,4,6-tri-O-acetyl-1-N-[N-(benzyloxycarbonyl)-L-aspart-1-oyl-(phenylalanine methyl ester)-4-oyl]-2-deoxy-β-D-glucopyranosylamine were synthesized by condensation of 2-acetamido-3,4,6-tri-O-acetyl-1-N-[N-(benzyloxycarbonyl)-L-aspart-4-oyl]-2-deoxy-β-D-glucopyranosylamine with the appropriate protected amino acids and tri- and tetra-peptides. The amino acid sequences of 21 and 22 correspond to the protected amino acid sequences 34–37 and 34–38 of ribonuclease B that are adjacent to the carbohydrate-protein linkage.     

Influence of Organic Pesticides on Nematode Populations and Seed Production of Centipede Grass

Applications of ethyl 4-(methylthio)-m-tolyl isopropylphosphoramidate, O,O-diethyl O-((p-(methylsulfinyl)phenyl) phosphorothioate, and O,O-diethyl S-[2-(ethylthio)ethyll phosphorotbioate effectively controlled Trichodorus christiei on centipede grass. Populations of Pratylenchus spp. and Xiphinema americanum were significantly reduced with a mixture of methanesulfonic acid, 2,4-dichlorophenyl ester and 1,2-dibromo-3-chloropropane. Ethyl 4-(methylthio)-m-tolyl isopropylphosphoramidate and O,O-diethyl O-((p-(methylsulfinyl)phenyl phosphorothioate significantly suppressed populations of Pratylenchus spp., and the latter reduced populations of X. arnericanum. Ethyl 4-(methylthio)-m-tolyl isopropylphosphoramidate and O,O-diethyl O-((p-methylsulfinyl) phenyl) phosphorothioate significantly reduced populations of Criconemoides ornatus. Increased seed production was correlated with nematode control.