Why did Nature select phosphate for its dominant roles in biology?

Bowler, Matthew W.; Cliff, Matthew J.; Waltho, Jonathan P.; Blackburn, G. Michael

doi:10.1039/b9nj00718k

Cited by 158 publications

(141 citation statements)

References 48 publications

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“…The lanthanide(III) ion complexes 4·La(III), 4·Eu(III) and 4·Tb (III) were formed by heating 4 at reflux with La(CF 3 SO 3 ) 3 , Eu (CF 3 SO 3 ) 3 , Tb(CF 3 SO 3 ) 3 respectively, in methanol overnight.…”

Section: Resultsmentioning

confidence: 99%

“…39 The 1 H NMR of ligand 5 was recorded at 50°C in order to fully elucidate the structure of the ligands. This ligand was then heated at reflux with 1.1 equivalents of either La(CF 3 SO 3 ) 3 or Eu(CF 3 SO 3 ) 3 in dry acetonitrile followed by precipitation from diethyl ether to yield 5·La(III) and 5·Eu(III), respectively. These complexes were purified in the same manner as those discussed above and were characterised by ESMS, HRMS, IR and NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

“…The lanthanide(III) ion complexes 6·La(III), 6·Eu(III), 7·La(III) and 7·Eu(III) were formed by heating either 6 or 7 at reflux with either La(CF 3 SO 3 ) 3 or Eu(CF 3 SO 3 ) 3 to yield water soluble complexes in varying yields. As expected the introduction of amino amide arms into the pseudo dipeptide structure increased the overall water solubility of these complexes.…”

Section: Resultsmentioning

confidence: 99%

“…42 The pH range of the titrations for the determination of the metal complex ion formation constants was limited due to the formation of hydroxide species. The titration curve of the protonated ligand 4, in the absence and presence of La(ClO 4 ) 3 and Eu(ClO 4 ) 3 against NEt 4 OH are represented in Fig. 2 (the titration curve of the protonated ligand 3, in the absence and presence of La(ClO 4 ) 3 and Eu(ClO 4 ) 3 against NEt 4 OH can be seen in the ESI † Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The titration curve of the protonated ligand 4, in the absence and presence of La(ClO 4 ) 3 and Eu(ClO 4 ) 3 against NEt 4 OH are represented in Fig. 2 (the titration curve of the protonated ligand 3, in the absence and presence of La(ClO 4 ) 3 and Eu(ClO 4 ) 3 against NEt 4 OH can be seen in the ESI † Fig. S4 for 3).…”

Section: Resultsmentioning

confidence: 99%

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Tri- and tetra-substituted cyclen based lanthanide(iii) ion complexes as ribonuclease mimics: a study into the effect of log K_a, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP)

2015

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A series of tetra-substituted 'pseudo' dipeptide ligands of cyclen (1,4,7,10,-tetraazacyclododecane) and a tri-substituted 3'-pyridine ligand of cyclen, and the corresponding lanthanide(III) complexes were synthesised and characterised as metallo-ribonuclease mimics. All complexes were shown to promote hydrolysis of the phosphodiester bond of 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP, τ 1/2 = 5.87 × 10 3 h), a well known RNA mimic. The La(III) and Eu(III) tri-substituted 3'-pyridine lanthanide(III) complexes being the most efficient in promoting such hydrolysis at pH 7.4 and at 37°C; with τ 1/2 = 1.67 h for La(III) and 1.74 h for Eu(III). The series was developed to provide the opportunity to investigate the consequences of altering the lanthanide(III) ion, coordination ability and hydrophobicity of a metallo-cavity on the rate of hydrolysis using the model phosphodiester, HPNP, at 37°C. To further provide information on the role that the log K a of the metal bound water plays in phosphodiester hydrolysis the protonation constants and the metal ion stability constants of both a tri and tetra-substituted 3'pyridine complex were determined.Our results highlighted several key features for the design of lanthanide(III) ribonucelase mimics; the presence of two metal bound water molecules are vital for pH dependent rate constants for Eu(III) complexes, optimal pH activity approximating physiological pH (∼7.4) may be achieved if the log K a values for both MLOH and ML(OH) 2 species occur in this region, small changes to hydrophobicity within the metallo cavity influence the rate of hydrolysis greatly and an amide adjacent to the metal ion capable of forming hydrogen bonds with the substrate is required for achieving fast hydrolysis.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 3 more Smart Citations

Tri- and tetra-substituted cyclen based lanthanide(iii) ion complexes as ribonuclease mimics: a study into the effect of log K_a, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP)

2015

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Pentacoordinate Phosphorus Compounds

2019

Organophosphorus Chemistry

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Novel, Stereoselective and Stereospecific Synthesis of Allenylphosphonates and Related Compounds via Palladium‐Catalyzed Propargylic Substitution

Kalek

Stawiński

2011

Adv Synth Catal

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Abstract:We have developed a novel method for the synthesis of allenylphosphonates and related compounds based on a palladium(0)-catalyzed reaction of propargylic derivatives with H-phosphonate, H-phosphonothioate, H-phosphonoselenoate, and Hphosphinate esters. The reaction is stereoselective and stereospecific, and provides a convenient entry to a vast array of allenylphosphonates and their analogues with diverse substitution patterns in the allenic moiety and at the phosphorus center. Some mechanistic aspects of this new reaction were also investigated.

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Why did Nature select phosphate for its dominant roles in biology?

Cited by 158 publications

References 48 publications

Tri- and tetra-substituted cyclen based lanthanide(iii) ion complexes as ribonuclease mimics: a study into the effect of log K_a, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP)

Tri- and tetra-substituted cyclen based lanthanide(iii) ion complexes as ribonuclease mimics: a study into the effect of log K_a, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP)

Pentacoordinate Phosphorus Compounds

Novel, Stereoselective and Stereospecific Synthesis of Allenylphosphonates and Related Compounds via Palladium‐Catalyzed Propargylic Substitution

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Why did Nature select phosphate for its dominant roles in biology?

Cited by 158 publications

References 48 publications

Tri- and tetra-substituted cyclen based lanthanide(iii) ion complexes as ribonuclease mimics: a study into the effect of log Ka, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP)

Tri- and tetra-substituted cyclen based lanthanide(iii) ion complexes as ribonuclease mimics: a study into the effect of log Ka, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP)

Pentacoordinate Phosphorus Compounds

Novel, Stereoselective and Stereospecific Synthesis of Allenylphosphonates and Related Compounds via Palladium‐Catalyzed Propargylic Substitution

Contact Info

Product

Resources

About

Tri- and tetra-substituted cyclen based lanthanide(iii) ion complexes as ribonuclease mimics: a study into the effect of log K_a, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP)

Tri- and tetra-substituted cyclen based lanthanide(iii) ion complexes as ribonuclease mimics: a study into the effect of log K_a, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP)