1,5-Hydride shift in Wolff-Kishner reduction of (20R)-3beta,20, 26-trihydroxy-27-norcholest-5-en-22-one: synthetic, quantum chemical, and NMR studies.

Heating (20R)-3beta,20,26-trihydroxy-27-norcholest-5-en-22-one (1) with hydrazine and KOH at 160 degrees C completely converted the steroid to a diastereoisomeric mixture of the new (20R,22RS)-27-norcholest-5-ene-3beta,20,22-triols (2). Exclusive formation of 2 suggests that the expected Wolff-Kishner reduction to a methylene group at the C-22 ketone in 1 was diverted to the C-26 position by a 1,5-hydride shift. All attempts under acid conditions failed to produce a C-22 phenyl hydrazone from 1. However, reaction of 1 was reacted with phenylhydrazine in hot KOH, gave the C-26 phenylhydrazone 4 as the sole product. Evidently, under alkaline conditions, first a hydride ion undergoes an intramolecular transfer from the C-26 CH(2)OH group to the C-22 ketone in 1, and then the phenylhydrazine traps the newly formed aldehyde. To examine this hypothesis, we constructed computer-simulated transition state models from quantum chemical calculations and then compared data from these models with NMR measurements of the reaction mixtures containing 2. The NMR data showed that the C-22 diastereoisomers of 2 are formed in a nearly 1:1 ratio exactly as predicted from the energy-optimized transition states, which were calculated for intramolecular 1,5-hydride shifts that produced each of the two C-22 diastereoisomers. Accordingly, these results support the hypothesis that an intramolecular 1,5-hydride shift mechanism promotes complete conversion of 1 to 2 under classical Wolff-Kishner reduction conditions.     

Study of elastic collisions of Myxococcus xanthus in swarms

In very low density situations where a single myxobacterial cell is isolated from direct contact with other cells, the slime capsule interaction with the substrate or slime tracks on the substrate produce a viscous drag that results in a smooth gliding motion. Viscoelastic interactions of myxobacteria cells in a low-density domain close to the edge of a swarm are studied using a combination of a cell-based three-dimensional computational model and cell-tracking experiments. The model takes into account the flexible nature of Myxococcus xanthus as well as the effects of adhesion between cells arising from the interaction of the capsular polysaccharide covering two cells in contact with each other. New image and dynamic cell curvature analysis algorithms are used to track and measure the change in cell shapes that occur as flexible cells undergo significant bending during collisions resulting in direct calibration of the model parameters. Like aspect-ratio and directional reversals, the flexibility of cells and the adhesive cell-cell and cell-substrate interactions of M. xanthus play an important role in smooth gliding and more efficient swarming.     

Structural studies on proteoglycan from human chondrosarcoma.

Proteoglycan was isolated from a human chondrosarcoma which contained all glycosaminoglycans found in articular cartilage. Proteoglycans extracted by associative (67% of total uronate) and subsequent dissociative (27% of total uronate) solvents were identical as assessed by chromatography on Sepharose 2B (K_av 0.43), electrophoresis on acrylamideagarose gels, and in their ability to bind to hyaluronate. In addition there were no differences in chondroitin sulfate size, ratio of chondroitin 4- to 6-sulfate, or in size or form of keratan sulfate present. Two forms of keratan sulfate were identified following treatment with alkaline borohydride: A larger species (～-23 monosaccharides) was isolated from the keratan sulfate-enriched region only; a smaller oligosaccharide (～-13 monosaccharides) was recovered from all peptidoglycans released by trypsin, chymotrypsin treatment.     

Repair of 3-methyladenine and 7-methylguanine in nuclear DNA of Chlamydomonas: Requirement for protein synthesis

The removal of 3-methyladenine and 7-methylguanine from nuclear DNA was determined following exposure of Chlamydomonas reinhardi to methyl methanesulfonate (MMS). The amount of 3-methyladenine in DNA was determined using an extract from Micrococcus luteus that has a 3-methyladenine-DNA glycosylase. The amount of 7-methylguanine was estimated by heating the DNA for 30 min at 70° followed by alkaline hydrolysis of the resulting apurinic sites. The molecular weight of the DNA was determined using alkaline sucrose gradients. The 3-methyladenine is removed with a half-life of 2–3 h whereas the 7-methylaguanine is removed with a half-life of 10–12 h. The rate of removal of the 7-methylguanine is more than an order of magnitude faster than the estimated non-enzymatic hydrolysis rate indicating the probability of enzymatic repair. Addition of cycloheximide immediately after MMS treatment inhibits the removal of 3-methyladenine and 7-methylguanine from DNA. If cycloheximide is added 1.5 h after treatment with MMS, there is much less inhibition of the removal of 3-methyladenine. These results are interpreted to mean that MMS induces the synthesis of 1 or more proteins that are required for the repair of 3-methyladenine from Chlamydomonas DNA.     

Social background and breastfeeding among American mothers

Using 1965 National Fertility Survey data, the national trends and patterns of breastfeeding among American mothers are examined. A review of the literature finds most results of studies to be inconsistent. In this study the total sample was 4918 mothers with first births. The general conclusion is that breastfeeding has been declining since the turn of the century. 50% breastfed their first child. Black and Latin American mothers are about 7 points above the average. Northwest European (English and German) mothers had higher rates than mothers from Irish, Slavic, French or Italian backgrounds. Being a Catholic makes a mother less likely to breastfeed her first baby for most all nationality groups except Latin American. Farm mothers were much more likely to have breastfed their first baby than nonfarm mothers, 64% to 49%. The South and West geographical districts were 6-8 points above the grand mean while the Midwest and Northeast are below it. Only 40% of mothers in the Northeast breastfeed. By education, the lowest educational category (6 years or less) have the highest breastfeeding rates, 74%, which declines to high school graduates who have a low of 44%, then rises with a college education. The college educated group is the next highest category after the lowest educated group. White collar workers and service employed were the highest groups among occupations of those breastfeeding.     

The effects of various temperature-salinity combinations on the body form of newly hatchedCyprinodon macularius (Teleostei)

Summary 1. Spawning groups of the teleostCyprinodon macularius kept at 28° C in air-saturated water of 35 salinity were allowed to spawn at intervals of 3 to 4 days. Their eggs were transferred 4 hours after fertilization into a variety of temperature-salinity combinations and the newly hatched young fixed within 60 minutes. The body form of these young was then examined by measuring 13 different length, depth and width dimensions.2. All 13 dimensions vary as a function of the temperature and salinity conditions effective during incubation. The dimension versus temperature plot results in differently shaped curves in the three test salinities.3. In fresh water, body length decreases above and below 32° to 33° C, while the various depth and width measurements increase. Maximum total length values are therefore correlated with minimum depth and width values; the body tends to become deeper and wider in the lowest and highest temperatures tested.4. In 35 body length decreases progressively with increasing temperature, especially near the upper critical temperature (34°, 35° C). All depth and width dimensions measured tend to decrease more or less harmoniously; hence there is little change in body form (isometry).5. In 70 body length decreases rapidly from 26° to 28° C but changes little in the next higher temperature level (31° C). All depth and width dimensions measured tend to change proportionally (often not quite as harmoniously as in 35 ).6. It seems possible that the increasing degree of disharmony in the order 35 < 70 < fresh water is related to the fact that(a) all eggs tested were laid and fertilized in 35 and remained there for 4 hours before being transferred into the test salinities and(b) 35 affords near optimum conditions for growth and reproduction. It seems possible that the structural consequences of exposure to the different incubation media may be different if spawning took place in fresh water or 70 instead of in 35 .7. Body depth and width tend to increase with decreasing salinity, resulting in rounder fish in fresh water with less surface area per unit volume.8. Body dimensions (length as well as depth and width) are significantly smaller in 70 than in fresh water or 35 .9. Changes in body dimensions of hatching fry may be related to the concomittant changes in the amounts of dissolved gases, especially O₂, in the various temperature and salinity combinations employed.10. Environmental effects during very early ontogeny are of paramount importance for the functional and structural properties of the individual and may modify its ecological capacities.

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Die Wirkungen verschiedener Temperatur-Salzgehalts Kombinationen auf die Körperform frischgeschlüpftercyprinodon macularius (Teleostei)

Kurzfassung Eier des KnochenfischesCyprinodon macularius wurden 4 Stunden nach dem Laichakt in verschiedene Temperatur-Salzgehalts Kombinationen überführt und unter kontrollierten Bedingungen erbrütet. Alle zum Laichen angesetzten Elterntiere besaßen einen ähnlichen genetischen Hintergrund (Nachkommen eines einzigen Ausgangspaares) und waren während ihres ganzen Lebens bei 28° C und 35 S gehalten worden. Die frischgeschlüpften Jungfische wurden möglichst rasch fixiert und 13 ihrer Körperdimensionen vermessen. — Alle vermessenen Dimensionen werden durch Temperatur und Salzgehalt des Inkubationsmediums beeinflußt. Trägt man die Dimensionen gegen die Inkubationstemperatur auf, so ergeben sich in den drei Testsalzgehalten unterschiedliche Kurvenzüge. In Süßwasser nimmt die Körperlänge von 28° bis 33° C zu, verringert sich aber merkbar bei 34° C; Körpertiefe und -breite verhalten sich praktisch umgekehrt; die größte Länge wird also bei einer intermediären Temperaturstufe erreicht und ist korreliert mit Minimalwerten für Tiefe und Breite (v-förmige Kurven); die größte Tiefe und Breite wird in den niedrigsten (28° C) und in den höchsten (34° C) Testtemperaturen erreicht. In 35 verringert sich die Körperlänge mit abnehmender Temperatur und sowohl die Tiefe als auch die Breite des Körpers verändern sich nahezu direkt proportional (weitgehend isometrisches Wachstum). In 70 nimmt die Körperlänge von 26° nach 28° C rapide ab, zeigt aber bei 31° C nur geringfügige Veränderungen; Tiefe und Breite verändern sich harmonisch; das Ausmaß der Isometrie ist jedoch zumeist geringer als in 35 . Mit abnehmendem Salzgehalt verringert sich der Oberflächen/Volumen-Quotient des Körpers. Die Befunde werden im Lichte früherer Untersuchungen anC. macularius und ähnlicher Studien an anderen aquatischen Organismen eingehend erörtert. Zweifellos kommt dem Einfluß der Umwelt — insbesondere während der sehr frühen Ontogenie — eine hervorragende Bedeutung zu für die funktionellen und strukturellen Eigenschaften und damit für die ökologische Potenz des aufwachsenden Individuums.