‘The role of organic molecules in molecular sieve synthesis’: Comment

Zeolites ◽  
1984 ◽  
Vol 4 (4) ◽  
pp. 402
Author(s):  
W.M. Meier
Zeolites ◽  
1983 ◽  
Vol 3 (4) ◽  
pp. 282-291 ◽  
Author(s):  
B.M. Lok ◽  
T.R. Cannan ◽  
C.A. Messina

1984 ◽  
Vol 15 (16) ◽  
Author(s):  
B. M. LOK ◽  
T. R. CANNAN ◽  
C. A. MESSINA

Author(s):  
Thomas Glonek

AbstractHow life began still eludes science life, the initial progenote in the context presented herein, being a chemical aggregate of primordial inorganic and organic molecules capable of self-replication and evolution into ever increasingly complex forms and functions.Presented is a hypothesis that a mineral scaffold generated by geological processes and containing polymerized phosphate units was present in primordial seas that provided the initiating factor responsible for the sequestration and organization of primordial life’s constituents. Unlike previous hypotheses proposing phosphates as the essential initiating factor, the key phosphate described here is not a polynucleotide or just any condensed phosphate but a large (in the range of at least 1 kilo-phosphate subunits), water soluble, cyclic metaphosphate, which is a closed loop chain of polymerized inorganic phosphate residues containing only phosphate middle groups. The chain forms an intrinsic 4-phosphate helix analogous to its structure in Na Kurrol’s salt, and as with DNA, very large metaphosphates may fold into hairpin structures. Using a Holliday-junction-like scrambling mechanism, also analogous to DNA, rings may be manipulated (increased, decreased, exchanged) easily with little to no need for additional energy, the reaction being essentially an isomerization.A literature review is presented describing findings that support the above hypothesis. Reviewed is condensed phosphate inorganic chemistry including its geological origins, biological occurrence, enzymes and their genetics through eukaryotes, polyphosphate functions, circular polynucleotides and the role of the Holliday junction, previous biogenesis hypotheses, and an Eoarchean Era timeline.


1968 ◽  
Vol 48 (3) ◽  
pp. 521-532
Author(s):  
J. E. PHILLIPS ◽  
A. A. DOCKRILL

1. The permeability of perfused intimal sacs to fourteen non-ionic, hydrophilic molecules of graded molecular size was estimated by radioisotope flux. 2. The rectal cuticle acts as a molecular sieve severely restricting the rate of penetration of molecules with increasing hydrated size. 3. The penetration of test molecules was as predicted by the Renkin equation for a uniform population of water-filled pores having radii of 6.5 Å. 4. The properties of cuticles from the rectum and the integument are compared and the role of the rectal intima in the excretory process in the desert locust is discussed.


Carbon ◽  
2020 ◽  
Vol 157 ◽  
pp. 385-394 ◽  
Author(s):  
Samuel S. Hays ◽  
Oishi Sanyal ◽  
Nicholas E. León ◽  
Pezhman Arab ◽  
William J. Koros

2019 ◽  
Vol 116 (9) ◽  
pp. 3419-3424
Author(s):  
Tian Zhou ◽  
Santanu Malakar ◽  
Steven L. Webb ◽  
Karsten Krogh-Jespersen ◽  
Alan S. Goldman

The insertion of CO into metal-alkyl bonds is the key C-C bond-forming step in many of the most important organic reactions catalyzed by transition metal complexes. Polar organic molecules (e.g., tetrahydrofuran) have long been known to promote CO insertion reactions, but the mechanism of their action has been the subject of unresolved speculation for over five decades. Comprehensive computational studies [density functional theory (DFT)] on the prototypical system Mn(CO)5(arylmethyl) reveal that the polar molecules do not promote the actual alkyl migration step. Instead, CO insertion (i.e. alkyl migration) occurs rapidly and reversibly to give an acyl complex with a sigma-bound (agostic) C-H bond that is not easily displaced by typical ligands (e.g. phosphines or CO). The agostic C-H bond is displaced much more readily, however, by the polar promoter molecules, even though such species bind only weakly to the metal center and are themselves then easily displaced; the facile kinetics of this process are attributable to a hydrogen bonding-like interaction between the agostic C-H bond and the polar promoter. The role of the promoter is to thereby catalyze isomerization of the agostic product of CO insertion to give an η2-C,O-bound acyl product that is more easily trapped than the agostic species. This ability of such promoters to displace a strongly sigma-bound C-H bond and to subsequently undergo facile displacement themselves is without reported precedent, and could have implications for catalytic reactions beyond carbonylation.


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