10 research outputs found
Problems of multi-species organisms: endosymbionts to holobionts
The organism is one of the fundamental concepts of biology and has been at the center of many discussions about biological individuality, yet what exactly it is can be confusing. The definition that we find generally useful is that an organism is a unit in which all the subunits have evolved to be highly cooperative, with very little conflict. We focus on how often organisms evolve from two or more formerly independent organisms. Two canonical transitions of this typeâreplicators clustered in cells and endosymbiotic organelles within host cellsâdemonstrate the reality of this kind of evolutionary transition and suggest conditions that can favor it. These conditions include co-transmission of the partners across generations and rules that strongly regulate and limit conflict, such as a fair meiosis. Recently, much attention has been given to associations of animals with microbes involved in their nutrition. These range from tight endosymbiotic associations like those between aphids and Buchnera bacteria, to the complex communities in animal intestines. Here, starting with a reflection about identity through time (which we call âTheseusâs fishâ), we consider the distinctions between these kinds of animalâbacteria interactions and describe the criteria by which a few can be considered jointly organismal but most cannot
Chelated Assisted Metal-Mediated NâH Bond Activation of ÎČâLactams: Preparation of Iridaâ, Rhodaâ, Osmaâ, and Ruthenatrinems
2-Azetidinones
substituted with pyridine (<b>2a</b>), quinoline
(<b>2b</b>), isoquinoline (<b>2c</b>), imidazole (<b>2d</b>), and benzimidazole (<b>2e</b>) at the 4-position
of the four-membered ring have been prepared in order to synthesize
tribactams containing a transition metal and its associated ligands,
L<sub><i>n</i></sub>M, at the 2-position of the tricyclic
skeleton. The developed procedure is compatible with a wide range
of transition-metal starting complexes. Thus, the iridium and rhodium
dimers [MÂ(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)ÂCl<sub>2</sub>]<sub>2</sub> react with <b>2a</b>â<b>e</b>, in
the presence of sodium acetate, to afford irida- and rhodatrinems
(<b>1a</b>â<b>j</b>) containing the half-sandwich
d<sup>6</sup> metal fragments MÂ(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Cl (M = Ir, Rh). The reactions of [MÂ(ÎŒ-OMe)Â(η<sup>4</sup>-COD)]<sub>2</sub> (M = Ir, Rh) with <b>2a</b> lead
to irida- and rhodatrinems (<b>1k</b>,<b>l</b>) with the
d<sup>8</sup> moieties MÂ(η<sup>4</sup>-COD). The coordination
sphere and oxidation state of the metal center in these compounds
can be modified, without affecting the 2-azetidinone backbone, by
means of substitution and oxidative addition reactions. As a proof
of concept, metallatrinems with the MÂ(CO)<sub>2</sub> (M = Ir (<b>1m</b>), Rh (<b>1n</b>)) and IrÂ(Me)ÂIÂ(CO)<sub>2</sub> (<b>1o</b>) units are also reported. Osmatrinems <b>1p</b>,<b>q</b> containing the d<sup>4</sup> metal fragment OsH<sub>3</sub>(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> have been obtained starting
from the d<sup>2</sup> hexahydride OsH<sub>6</sub>(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub>, by reaction with <b>2a</b>,<b>b</b>, whereas the treatment of the tetrahydroborate complexes MHÂ(η<sup>2</sup>-H<sub>2</sub>BH<sub>2</sub>)Â(CO)Â(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (M = Os, Ru) with <b>2a</b> yields osma- and
ruthenatrinems (<b>1r</b>,<b>s</b>) containing six-coordinate
bisÂ(phosphine) d<sup>6</sup> metal fragments. The IR stretching frequency
of the lactamic carbonyl, the bent angle between the five- and four-membered
rings of the tricycle, and the NâCO bond length in the lactamic
ring are clearly infuenced by the L<sub><i>n</i></sub>M
fragment