ABSTRACT
The title compound {systematic name: (1R,4S,4aS,7R,8aR)-4-bromo-7-[(1S,3R)-3-bromo-1,2,2-trimethyl-cyclo-pent-yl]-1,4a-dimethyl-deca-hydro-naphthalene-1,7,8a-triol}, C(20)H(34)Br(2)O(3), is a neoirieane-type bromo-diterpenoid isolated from Laurencia yonaguniensis Masuda et Abe, species inedita. The absolute stereochemistry was established as (1S,4R,5R,7R,10S,11S,14R). The structure displays inter- and intra-molecular O-Hâ¯O hydrogen bonding.
ABSTRACT
The production of labeled brominated metabolites with radioactive (82)Br in Laurencia species was investigated as part of a study of the biosynthesis of halogenated metabolites from species belonging to the red algal genus Laurencia (Rhodomelaceae, Ceramiales). Radiobromide [(82)Br], thin-layer chromatography (TLC), and TLC-autoradioluminography (ARLG) were used. When cultured in artificial seawater medium (ASP(12)NTA including Na(82)Br) under 16:8 h light:dark (LD) illumination cycles for 24 h, each of the strains of Laurencia, Laurencia japonensis Abe et Masuda, Laurencia nipponica Yamada (laurencin-producing race and laureatin-producing race), and Laurencia okamurae Yamada, produced species- (or race-) specific (82)Br-containing metabolites. In the case of the laurencin-producing race of L. nipponica, laurencin and deacetyllaurencin were found to be produced in approximately 1:1 ratio, though laurencin is the major metabolite in the wild sample. Furthermore, when cultured in the dark, the production rates of brominated metabolites in Laurencia spp. were found to be diminished. The present study strongly indicates that the use of radiobromine [(82)Br] in combination with the TLC-ARLG method is an effective approach for investigating the biosynthesis of brominated metabolites in Laurencia.
Subject(s)
Bromine Radioisotopes/metabolism , Chromatography, Thin Layer , Hydrocarbons, Brominated/metabolism , Laurencia/metabolism , Oxocins/metabolism , Autoradiography , Darkness , Isotope LabelingABSTRACT
During our studies on Malaysian Laurencia species, brominated metabolites, tiomanene, acetylmajapolene B, and acetylmajapolene A were isolated from an unrecorded species collected at Pulau Tioman, Pahang along with known majapolene B and majapolene A. Acetylmajapolene A was a mixture of diastereomers as in the case of majapolene A. Tiomanene may be a plausible precursor for acetylmajapolenes B and A. In addition, three known halogenated sesquiterpenes and two known halogenated C(15) acetogenins were found from other two unrecorded species collected at Pulau Karah, Terengganu and Pulau Nyireh, Terengganu, respectively. Some of these halogenated metabolites showed moderate antibacterial activity against some marine bacteria.
Subject(s)
Anti-Bacterial Agents/isolation & purification , Anti-Bacterial Agents/pharmacology , Laurencia/chemistry , Sesquiterpenes/isolation & purification , Sesquiterpenes/pharmacology , Acetylation , Anti-Bacterial Agents/chemistry , Chromobacterium/drug effects , Erwinia/drug effects , Halogenation , Malaysia , Microbial Sensitivity Tests , Molecular Structure , Proteus/drug effects , Sesquiterpenes/chemistry , Vibrio/drug effectsABSTRACT
Further investigation of Laurencia species from Japanese waters, which were collected at three locations, yielded brominated metabolites, a labdane- type diterpene and a C15 acetogenin possessing a terminal bromoallene group. Their structures were deduced from analysis of spectroscopic data.
Subject(s)
Diterpenes/chemistry , Fatty Alcohols/chemistry , Halogens/metabolism , Lactones/chemistry , Laurencia/chemistry , Acetogenins , Diterpenes/metabolism , Fatty Alcohols/metabolism , Halogens/chemistry , Japan , Lactones/metabolism , Laurencia/metabolism , Magnetic Resonance Spectroscopy , Molecular StructureABSTRACT
We performed an investigation of medication notebook utilization among patients in Iwai City and conducted a questionnaire survey of physicians to evaluate its usefulness. The patients who used our insurance pharmacies for dispensing prescriptions were queried about six items, i.e., age, types of acute or chronic disease, possession of a medication notebook, efficient use of a medication notebook, consultation at two or more medical institutions, and efficient use of the medication notebook at the other medical institutions. The medication notebook possession rates were 73.1% and 94.6% among those aged 69 years or younger and among those aged 70 years or older, respectively. Furthermore, one patients who unified their drug information from two or more medical institutions into one medication notebook accounted for 55.4% and 73.2% of patients with chronic diseases aged 69 years or younger and those aged 70 years or older, respectively. As a result of the questionnaire survey, 92.3%, 76.9%, and 69.2% of physicians evaluated the medication notebook favorably in preventing duplicate prescriptions, avoiding drug interactions, and deferminins side effects due to prescriptions from other medical institutions, respectively. To increase the effective use of the medication notebook in patients with chronic diseases aged 69 years or younger, we need to promote an educational campaign instructing them in its clinical usefulness.
Subject(s)
Drug Information Services/statistics & numerical data , Aged , Humans , Japan , Pharmacies , Surveys and QuestionnairesABSTRACT
Two halogenated C(15) acetogenins, itomanallenes A and B, with a terminal bromoallene moiety along with a halogenated sesquiterpene, itomanol, have been isolated from the red alga Laurencia intricata collected in Okinawan waters. Their structures were deduced from 1D and 2D NMR experiments including (1)H-(1)H COSY, HSQC, HMBC, and NOESY methods. The alcohol corresponding to itomanallene B seems to be a plausible precursor of itomanallene A, which has an unusual 2,10-dioxabicyclo[7.3.0]dodecene skeleton. Itomanol was found to be a selinane-type bromosesquiterpenoid, and is the first example of a selinane to be isolated from Japanese Laurencia species.
Subject(s)
Bromine/metabolism , Heterocyclic Compounds, 2-Ring/isolation & purification , Rhodophyta/metabolism , Sesquiterpenes/isolation & purification , Heterocyclic Compounds, 2-Ring/chemistry , Molecular Structure , Sesquiterpenes/chemistry , Spectrum AnalysisABSTRACT
From an unidentified species of Laurencia collected from Okinawan waters two novel brominated metabolites, 1 and 2, along with known halogenated compounds, 2,10-dibromo-3-chloro-alpha-chamigrene (3) and microcladallene A (4), were isolated and identified. The structures of these new compounds were established as ent-labdane-type bromoditerpenes, (1S,3R,5S,6S,8S,9S,10R,13R)-1-acetoxy-3-bromo-6-hydroxy-8,13-epoxy-labd-14-ene (1) and (3R,5S,6S,8S,9S,10R,13R)-3-bromo-6-hydroxy-8,13-epoxylabd-14-en-1-one (2), by interpretation of their spectroscopic data as well as by X-ray crystallographic analysis.
Subject(s)
Diterpenes/isolation & purification , Hydrocarbons, Brominated/chemistry , Hydrocarbons, Brominated/isolation & purification , Rhodophyta/chemistry , Crystallography, X-Ray , Diterpenes/chemistry , Diterpenes/pharmacology , Escherichia coli/drug effects , Hydrocarbons, Brominated/pharmacology , Japan , Molecular Conformation , Molecular Structure , Nuclear Magnetic Resonance, Biomolecular , Pseudomonas/drug effects , Salmonella/drug effects , Sesquiterpenes/chemistry , Sesquiterpenes/isolation & purification , Sesquiterpenes/pharmacology , Spectrophotometry, Infrared , Staphylococcus/drug effects , StereoisomerismABSTRACT
A novel brominated diterpene based on the rare neoirieane skeleton, named neoirietetraol (1), has been isolated along with a halogenated C15 acetogenin, (3Z)-laurenyne (2), from a new Laurencia species, L.yonaguniensis Masuda et Abe, species inedita, collected at Yonaguni Island, Okinawa Prefecture, Japan. The structures of these metabolites were elucidated by spectroscopic data (IR, 1H NMR, 13C NMR, 2D NMR, and MS). Neoirietetraol (1) was toxic to the brine shrimp (Altemia salina; LC50, 40.1 microM) and also showed weak antibacterial activities against two marine bacteria, Alcaligenes aquamarinus and Escherichia coli.
