Isolation of a benzene valence isomer with one-electron phosphorus-phosphorus bonds

A tetraphosphabenzene analog of the postulated anti-tricyclohexylene, a singlet biradical valence isomer of benzene, has been isolated. The tricyclic derivative features one-electron phosphorus-phosphorus bonds, which result from the pi*-pi* interaction between two diphosphirenyl radicals. Such one-electron bonds may play a wider role in phosphorus chemistry.     

Two types of somatostatin receptors differentiated by cyclic somatostatin analogs

Somatostatin receptors in rat brain, pituitary, and pancreas were labeled with two radioiodinated analogs of somatostatins 14 and 28. Two cyclic analogs of somatostatin, SMS201-995 and cyclo(Ala-Cys-Phe-D-Trp-Lys-Thr-Cys), showed biphasic displacement of binding to somatostatin receptors by these radioligands. In contrast, all other somatostatin analogs, including somatostatin-14, competed for the receptor sites with monophasic displacement of radioligand receptor binding. Thus two types of somatostatin receptors were identified. It was found that the pituitary and pancreas have predominantly one type of somatostatin receptor whereas the brain has both, and that different regions of the brain have various proportions of the two types. These findings suggest methods to characterize other types of somatostatin receptors subserving somatostatin's diverse physiological functions, including a potential role in cognitive function and extrapyramidal motor system control.     

Juvenile hormone analogs: a possible case of mistaken identity?

Many synthetic compounds that exhibit activity in juvenile hormone assays have limited structural resemblance to natural juvenile hormones. The observed morphogenic action of many of the compounds considered to be biologically analogous to juvenile hormones is probably synergistic rather than intrinsically hormonal.     

A cyclic model of the universe

We propose a cosmological model in which the universe undergoes an endless sequence of cosmic epochs that begin with a "bang" and end in a "crunch." Temperature and density at the transition remain finite. Instead of having an inflationary epoch, each cycle includes a period of slow accelerated expansion (as recently observed) followed by contraction that produces the homogeneity, flatness, and energy needed to begin the next cycle.     

Fluorocitrate inhibition of aconitase: relative configuration of inhibitory isomer by x-ray crystallography

The fluorocitrate isomer that is a strong inhibitor and inactivator of aconitase has been shown by x-ray crystallographic studies on the rubidium ammonium salt to have the configurations (1R : 2R) or (1S : 2S) 1-fluoro-2-hydroxy-1,2,3-propanetricarboxylic acid. A possible mechanism for the action of fluorocitrate is proposed which involves the 1R : 2R isomer suggested from biochemical data.     

Insect sex pheromones: minor amount of opposite geometrical isomer critical to attraction

(Z)-II-Tetradecenyl acetate is the reported sex pheromone of European corn borer and redbanded leafroller moths. However, geometrically pure preparations of the compound are weakly attractive to these species. Presence of the E geometrical isomer in the Z is necessary for maximum sex attraction and these moths are "tuned" to respond optimally to specific proportions of Z to E. This discovery is important to considerations of moth pheromonal specificity, evolution, and in application of knowledge of the pheromones to insect-pest suppression.     

Sex pheromone of the pink bollworm moth: biological masking by its geometrical isomer

A mixture of the cis and trans forms of propylure (10-propyl-trans-5,9-tridecadienyl acetate), the sex pheromone of the female pink bollworm moth, has been separated into its pure isomers by thin-layer chromatography. The cis isomer inhibits or masks the activity of the trans isomer, as little as 15 percent of the cis isomer being sufficient to completely nullify the activity of the trans isomer.     

Hycanthone analogs: dissociation of mutagenic effects from antischistosomal effects

N-Oxidation at the diethylamino group of hycanthone, of lucanthone, and of two chlorobenzothiopyranoindazoles resulted in a marked reduction in mutagenic activity, while antischistosomal activity was retained or even enhanced. Introduction of chlorine into the 8-position of benzothiopyranoindazoles reduced acute toxicity but had no effect on chemnotherapeutic potency. These dissociations of biological activities indicate that safer antischistosomal compounds of this class can be developed.     

Ecdysones and analogs: effects on development and reproduction of insects

Ingestion of certain synthetic ecdysone analogs inhibited larval growth and development in several species of insects, whereas 20-hydroxyecdysone was inactive or considerably less active. Natural 20-hydroxyecdysone and ponasterone A, and a synthetic ecdysone analog inhibited ovarian maturation and egg production in the adult housefly. These effects appeared to be related to hormonal activity.     

Puromycin analogs: action of adrenocorticotropic hormone and the role of glycogen

The effect of the injection into rats of analogs of puromycin, 6-dimethylaminopurine, and the aminonucleoside of puromycin on the stimullation of steroidogenesis by adrenocorticotropic hormone was coin pared with that of puromycin and cycloheximide. This stimulation was blocked only by the antibiotics, which also inhibited adrenal protein synthesis. Glycogenolysis is not associated with the primary mechanism of the adrenocorticotropic hormone stimnulation of steroid hormone biosynthesis in rats.     

Structure of pressinoic acid: the cyclic moiety of vasopressin

Arginine vasopressin consists of a 20-membered, disulfide-linked macrocyclic ring system called pressinoic acid to which is attached a COOH-terminal tripeptide. The molecular conformation of pressinoic acid has been determined from single crystal x-ray diffraction data. The 20-membered macrocyclic ring, stabilized by two intramolecular hydrogen bonds, has a type I beta-bend centered on Gln4 and Asn5 and a highly distorted type II' bend centered on Phe3 and Gln4. In vasopressin the Asn5 side chain extends away from the macrocyclic ring system and hydrogen bonds to the terminal tripeptide, but in pressinoic acid the Asn5 side chain lies over the molecule and forms a strong hydrogen bond to the nitrogen of Tyr2. The absence of pressor activity in pressinoic acid may be a result of both the loss of the COOH-terminal tripeptide and the incorrect orientation of the Asn5 side chain. Whether this class of hormones has pressor or oxytocic activity is determined by the orientation of the Tyr2 side chain, that is, whether it is extended away from or over the ring system, respectively. In pressinoic acid, the Tyr2 side chain is in the expected "pressor conformation," that is, extended away from the ring system, and is stabilized through a hydrophobic interaction with the Phe3 side chain. Thus, the conformation of the pressinoic acid molecule partly explains the activity of vasopressin-like hormones.     

The agulhas current during the late pleistocene: analysis of modern faunal analogs

Analysis of micropaleontologic evidence in a deep-sea core in the south-west Indian Ocean indicates that the Agulhas Current was not a dominant feature of this region during glacial intervals. Interpretation of the fossil record, based on the analysis of modern faunal analogs, indicates that during glacial intervals the Agulhas Current was not the strong, year-round current that it is today. Evidence shows that during summer months a weak tropical current was present. During winter months the current was replaced by cool, high-salinity waters. This interpretation suggests that seasonal changes in circulation may have been more pronounced in the southwest Indian Ocean during glacial intervals than today.     

Regulation of phosphodiesterase synthesis: requirement for cyclic adenosine monophosphate-dependent protein kinase

Endogenous cyclic adenosine monophosphate (AMP) and its dibutyryl derivative increase cyclic AMP phosphodiesterase activity in cultured lymphoma cells. This effect is prevented by cycloheximide. A variant population of cells deficient in cyclic AMP-dependent protein kinase contains lower basal phosphodiesterase activity, which cannot be induced by cyclic AMP.     

Pineal gland: dibutyryl cyclic adenosine monophosphate stimulation of labeled melatonin production

In organ cultures of intact rat pineal glands, N(6)O(2')-dibutyryl adenosine 3', 5'-monophosphate stimulates the conversion of tritiated trytophan to tritiated melatonin, as does L-norepinephrine. Potential sites of stimulation of melatonin production by dibutyryl cyclic adenosine monophosphate are discussed, based on observations that the dibutyryl analog also stimulates the conversion of serotonin labeled with carbon-14 to carbon-14-labeled melatonin without altering hydroxyin-dole-O-methyl transferase activity or intracellular accumulation of serotonin labeled with carbon-14.     

Biosynthesis of biopterin: adrenergic cyclic adenosine monophosphate-dependent inhibition in the pineal gland

Pineal glands in organ culture synthesize and release biopterin and are able to maintain concentrations of biopterin occurring in vivo for up to 54 hours in vitro. The intracellular biopterin content is reduced 50 percent by treatment with l-norepinephrine or cyclic adenosine monophosphate derivatives, but not by d-norepinephrine. This is an indication that biopterin levels are regulated by an adrenergic cyclic adenosine monophosphate-dependent mechanism. The decline in tissue biopterin content, produced mainly by inhibited of biosynthesis, is maximal at 6 hours and is not associated with either an increase in biopterin release or a shift in the reduction state of the biopterin.     

Nerve growth factor: relationship to the cyclic AMP system of sensory ganglia

Nerve growth factor and N(6),O(2)' dibutyryl adenosine 3',5'-monophosphate both stimulate neurite elongation by explanted ganglia. However, the addition of nerve growth factor does not lead to increased amounts of adenosine 3',5'-monophosphate in intact ganglia, nor does it stimulate adenylate cyclase activity in broken ganglia cells.     

Formation of cyclic water hexamer in liquid helium: the smallest piece of Ice

The cyclic water hexamer, a higher energy isomer than the cage structure previously characterized in the gas phase, was formed in liquid helium droplets and studied with infrared spectroscopy. This isomer is formed selectively as a result of unique cluster growth processes in liquid helium. The experimental results indicate that the cyclic hexamer is formed by insertion of water molecules into smaller preformed cyclic complexes and that the rapid quenching provided by the liquid helium inhibits its rearrangement to the more stable cage structure.     

Noradrenergic stimulation of cyclic adenosine monophosphate in rat Purkinje neurons: an immunocytochemical study

A specific immunofluorescent histochemical method for cyclic adenosine monophosphate was used to study rat cerebellum. After topical treatment with norepinephrine or stimulation of norepinephrine-containing afferents from locus coeruleus, there was a striking increase in the number of Purkinje cells with strong cyclic adenosine monophosphate reactivity. Other putative inhibitory transmitters had no significant effect on staining of Purkinje cells. The results provide the first histochemical support for the hypothesis that cyclic adenosine monophosphate can be generated postsynaptically in central neurons in response to noradrenergic stimuli.