Cruise Report 61-S-3 Albacore

(PDF contains 1 page.)

Cruise report 61-S-7 shrimp and crab

(PDF contains 7 pages.)

Cruise report 61-S-8 rockfish

(PDF contains 3 pages.)

Palladium-catalyzed asymmetric allylic alkylation: insights, application toward cyclopentanoid and cycloheptanoid molecules, and the total synthesis of several daucane sesquiterpenes

The asymmetric construction of quaternary stereocenters is a topic of great interest in the organic chemistry community given their prevalence in natural products and biologically active molecules. Over the last decade, the Stoltz group has pursued the synthesis of this challenging motif via a palladium-catalyzed allylic alkylation using chiral phosphinooxazoline (PHOX) ligands. Recent results indicate that the alkylation of lactams and imides consistently proceeds with enantioselectivities substantially higher than any other substrate class previously examined in this system. This observation prompted exploration of the characteristics that distinguish these molecules as superior alkylation substrates, resulting in newfound insights and marked improvements in the allylic alkylation of carbocyclic compounds.

General routes to cyclopentanoid and cycloheptanoid core structures have been developed that incorporate the palladium-catalyzed allylic alkylation as a key transformation. The unique reactivity of α-quaternary vinylogous esters upon addition of hydride or organometallic reagents enables divergent access to γ-quaternary acylcyclopentenes or cycloheptenones through respective ring contraction or carbonyl transposition pathways. Derivatization of the resulting molecules provides a series of mono-, bi-, and tricyclic systems that can serve as valuable intermediates for the total synthesis of complex natural products.

The allylic alkylation and ring contraction methodology has been employed to prepare variably functionalized bicyclo[5.3.0]decane molecules and enables the enantioselective total syntheses of daucene, daucenal, epoxydaucenal B, and 14-p-anisoyloxydauc-4,8-diene. This route overcomes the challenge of accessing β-substituted acylcyclopentenes by employing a siloxyenone to effect the Grignard addition and ring opening in a single step. Subsequent ring-closing metathesis and aldol reactions form the hydroazulene core of these targets. Derivatization of a key enone intermediate allows access to either the daucane sesquiterpene or sphenobolane diterpene carbon skeletons, as well as other oxygenated scaffolds.

A cocktail of thermally stable, chemically synthesized capture agents for the efficient detection of anti-gp41 antibodies from human sera and techniques

This thesis reports on a method to improve in vitro diagnostic assays that detect immune response, with specific application to HIV-1. The inherent polyclonal diversity of the humoral immune response was addressed by using sequential in situ click chemistry to develop a cocktail of peptide-based capture agents, the components of which were raised against different, representative anti-HIV antibodies that bind to a conserved epitope of the HIV-1 envelope protein gp41. The cocktail was used to detect anti-HIV-1 antibodies from a panel of sera collected from HIV-positive patients, with improved signal-to-noise ratio relative to the gold standard commercial recombinant protein antigen. The capture agents were stable when stored as a powder for two months at temperatures close to 60°C.

Fluorescence microscopy of nicotinic acetylcholine receptors

Neuronal nicotinic acetylcholine receptors (nAChRs) are pentameric ligand gated ion channels abundantly expressed in the central nervous system. Changes in the assembly and trafficking of nAChRs are pertinent to disease states including nicotine dependence, autosomal dominant nocturnal frontal lobe epilepsy (ADNFLE), and Parkinson’s disease (PD). Here we investigate the application of high resolution fluorescence techniques for the study of nAChR assembly and trafficking. We also describe the construction and validation of a fluorescent α5 subunit and subsequent experiments to elucidate the cellular mechanisms through which α5 subunits are expressed, assembled into mature receptors, and trafficked to the cell surface. The effects of a known single nucleotide polymorphism (D398N) in the intracellular loop of α5 are also examined.

Additionally, this report describes the development of a combined total internal reflection fluorescence (TIRF) and lifetime imaging (FLIM) technique and the first application of this methodology for elucidation of stochiometric composition of nAChRs. Many distinct subunit combinations can form functional receptors. Receptor composition and stoichiometry confers unique biophysical and pharmacological properties to each receptor sub-type. Understanding the nature of assembly and expression of each receptor subtype yields important information about the molecular processes that may underlie the mechanisms through which nAChR contribute to disease and addiction states.

Generation time and utilization of energy by aquatic bacteria. [Translation from: Trudy Instituta Biologii Vnutrennykh Vodnany 11(14), 198-202, 1966.]

Recent research has shown that the biomass of bacteria in lakes and other water-bodies can attain significant values. The huge production of bacteria is brought about by their great rate of reproduction. In a series of cases their biomass exceeds the biomass of phytoplankton. Therefore in a study of the biological productivity of water bodies it is necessary to calculate the biomass and production not only of the phyto- and zooplankton, but also of bacteria.The authors uses different methods and formulae to to compare the time of one generation of the bacteria.

On a method of determination of chlorophyll in cells of algae collected on a membrane filter. [Translation from: Trudy Instituta Biologii Vnutrennykh Vodnany 11(14), 198-202, 1966.]

The original method, proposed by Yentsch (1957), of determination of chlorophyll directly in the cells, attracts attention by its simplicity. In order to measure the content of chlorophyll by this method, a determined volume of suspension of algae is filtered through a membrane filter. The latter is dried a little, clarified by immersion oil, clamped between two glasses, and spectrophotometrized. Extinction is read off at , wavelengths equal to 670 millimicrons (around the maximum absorption of chlorophyll a in the cell) and 750 millimicrons (correction for non- specific absorption and dispersion of light by particles of the preparation). The method of Yentsch was employed by the authors for determination of chlorophyll-a in samples of phytoplankton. They conclude that in spite of the simplicity and convenience of determination the method must be applied sufficiently carefully. It is more suitable for analysis of cultures of algae, where, non-specific absorption of light is insignificant.

Rhythms of division of some algae in situ and in laboratory culture. [Translation from: Studii Cerc.Biol.(Bot.) 21, 61-65, 1969. ]

The rhythm of division of 9 species belonging to different groups of algae were analysed in situ and in the laboratory. The research which developed in different environmental conditions attempted to establish the capacity for multiplication and assimilation of chlorophyll on the part of the algae under study with a view to placing them in a culture. The results obtained showed that the green multicellular algae (eg. Ulothrix) and the blue algae (eg. Lyngbya, Oscillatoria) are able to produce an appreciable quantity of dry matter, just as the unicellular algae. At the same time it arises that amongst the numerous factors of the environment, temperature plays one of the most important roles in the process of multiplication.

Study on the dynamics of the population of a copepod (Eudiaptomus vulgaris Schmeil). [Translation from: Memorie dell'Istituto Italiano di Idrobiologia Dott.Marco de Marchi 13 179-202, 1961. ]

Eudiaptomus vulgaris Schmeil is the most abundant copepod in Lake Maggiore and forms also, in respect to other entomostraca, the most important element, through its average biomass and because it is fairly numerous throughout the year. Plankton samples collected in a systematic and quantitative way, gave the opportunity to study some aspects of the dynamics of the population of this copepod, in safety in view of the uncertainty which in this kind of study can ensue when samples are taken only at a single station - in consequence of the changes in size of population between different water masses. The results of the biometrical observations are of the population of Eudiaptomus vulgaris is presented.

Enantioselective Total Synthesis of Diketopiperazinecontaining Natural Products: (–)-Lansai B, (+)-Nocardioazines A and B, and (–)-Acetylapoaranotin

Diketopiperazine (DKP) motif is found in a wide range of biologically active natural products. This work details our efforts toward two classes of DKP-containing natural products.

Class one features the pyrroloindoline structure, derived from tryptophans. Our group developed a highly enantioselective (3 + 2) formal cycloaddition between indoles and acrylates to provide pyrroloindoline products possessing three stereocenters. Utilizing this methodology, we accomplished asymmetric total synthesis of three natural products: (–)-lansai B, (+)-nocardioazines A and B. Total synthesis of (–)-lansai B was realized in six steps, and featured an amino acid dimerization strategy. The total synthesis of (+)-nocardioazine B was also successfully completed in ten steps. Challenges were met in approaching (+)-nocardioazine A, where a seemingly easy last-step epoxidization did not prove successful. After re-examining our synthetic strategy, an early-stage epoxidation strategy was pursued, which eventually yielded a nine-step total synthesis of (+)-nocardioazine A.

Class two is the epidithiodiketopiperazine (ETP) natural products, which possesses an additional episulfide bridge in the DKP core. With the goal of accessing ETPs with different peripheral structures for structure-activity relationship studies, a highly divergent route was successfully developed, which was showcased in the formal synthesis of (–)-emethallicin E and (–)-haematocin, and the first asymmetric synthesis of (–)-acetylapoaranotin.

On the formation of ephippia in some Cladocera (Crustacea) [Translation from: Zoologicheskie Zhurnal 61, 1425-1427, 1982]

The determination of relative connections between families and genera of Cladocera, necessary for the construction of their natural systems, must be based on various criteria, among them on the structure of the ephippia. Of particular interest is the study of the process of formation and structure of the ephippium in Macrothricidae, different representatives of which differ significantly among themselves according to this criterion. In this article are presented the results of an investigation of the features of formation of the ephippium in seven species of Macrothricidae and in the moinid Moina weismanni Ishikawa (Moinidae).

Investigations of the sand movements in the district of the Elbe estuary [Translation from: Hamburger Kuestenforschung 19, [pages 61-63 only], 1975]

The present work is concerned with the processes of sand movement in the region of the Elbe estuary. In the first part the results of various investigations which have given indications of the regional transport directions are collected together. The interpretation of the results of a large number of continuous current recordings gives a picture of the resulting transport to be expected under the influence of the tides with those current conditions. This partial translation of the original paper provides the summary of this paper the regional distribution of the flood and ebb flow zones.

The content of organic matter in some waters in the Moscow region [Translation from: C.R. Acad. Soc. URSS, 61, 293-296, 1948]

There is at the moment no direct method of determining the organic matter content of natural waters. In 1940/41 8 different water bodies in central Russia were studied and their organic matter identified. The author concludes that there is currently no easy method to determine organic matter in water. A number methods need to be applied.

Front pages with contents of No. 61, 2000

Front cover. Table of Contents.