Photorelease of Primary Aliphatic and Aromatic Amines by Visible-Light-Induced Electron Transfer

Edson, Joseph B.; Spencer, Liam; Boncella, James M.

doi:10.1021/ol202456d

Cited by 51 publications

(40 citation statements)

References 45 publications

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“…40 The picolinium carbamate protecting group is stable in neutral aqueous solution and achieves high protection yields for primary, secondary, and aromatic amines. Deprotection is…”

Section: ■ Introductionmentioning

confidence: 99%

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Phototriggered DNA Phosphoramidate Ligation in a Tandem 5′-Amine Deprotection/3′-Imidazole Activated Phosphate Coupling Reaction

Cape¹,

Edson²,

Spencer³

et al. 2012

Bioconjugate Chem.

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We report the preparation and use of an N-methyl picolinium carbamate protecting group for applications in a phototriggered nonenzymatic DNA phosphoramidate ligation reaction. Selective 5'-amino protection of a modified 13-mer oligonucleotide is achieved in aqueous solution by reaction with an N-methyl-4-picolinium carbonyl imidazole triflate protecting group precursor. Deprotection is carried out by photoinduced electron transfer from Ru(bpy)(3)(2+) using visible light photolysis and ascorbic acid as a sacrificial electron donor. Phototriggered 5'- amino oligonucleotide deprotection is used to initiate a nonenzymatic ligation of the 13-mer to an imidazole activated 3'-phospho-hairpin template to generate a ligated product with a phosphoramidate linkage. We demonstrate that this methodology offers a simple way to exert control over reaction initiation and rates in nonenzymatic DNA ligation for potential applications in the study of model protocellular systems and prebiotic nucleic acid synthesis.

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“…40 The picolinium carbamate protecting group is stable in neutral aqueous solution and achieves high protection yields for primary, secondary, and aromatic amines. Deprotection is…”

Section: ■ Introductionmentioning

confidence: 99%

“…40 The picolinium carbamate protecting group is stable in neutral aqueous solution and achieves high protection yields for primary, secondary, and aromatic amines. Deprotection is achieved by visible light photoinduced electron transfer from Ru(bpy) 3 2+ using ascorbic acid as a sacrificial electron donor.…”

Section: ■ Introductionmentioning

confidence: 99%

Phototriggered DNA Phosphoramidate Ligation in a Tandem 5′-Amine Deprotection/3′-Imidazole Activated Phosphate Coupling Reaction

Cape¹,

Edson²,

Spencer³

et al. 2012

Bioconjugate Chem.

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“…In their originally conceived form, LANL's artificial cells were to consist of a micelle acting as the container, a light driven metabolism, and a genetic system, whose functions were all very tightly coupled (Cape et al 2011;DeClue et al 2009;Edson et al 2011;Maurer et al 2009Maurer et al , 2011Rasmussen et al 2008). The proposed container was to consist of amphiphilic fatty acid (FA) molecules that self-assembled into a micelle.…”

Section: Definition Of Photoactive Prebiotic Kernel Systemsmentioning

confidence: 99%

“…The active components of the systems synthesized at LANL and in the Center for Fundamental Living Technology (FLinT) at the University of Southern Denmark (SDU) (Cape et al 2011;DeClue et al 2009;Edson et al 2011;Maurer et al 2009Maurer et al , 2011Rasmussen et al 2008) contain on the order of one thousand atoms. We have investigated various features of these LANL synthesized derivatives starting from self-assembly of component molecules, the absorption of light, and the metabolism using quantum mechanical methods including electron correlation effects (Tamulis et al 2006(Tamulis et al , 2008(Tamulis et al , 2012(Tamulis et al , 2013(Tamulis et al , 2014Tamulis and Tamulis 2007a, b).…”

Section: Definition Of Photoactive Prebiotic Kernel Systemsmentioning

confidence: 99%

Quantum entanglement in photoactive prebiotic systems

Tamulis

Grigalavicius

2014

Syst Synth Biol

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This paper contains the review of quantum entanglement investigations in living systems, and in the quantum mechanically modelled photoactive prebiotic kernel systems. We define our modelled self-assembled supramolecular photoactive centres, composed of one or more sensitizer molecules, precursors of fatty acids and a number of water molecules, as a photoactive prebiotic kernel systems. We propose that life first emerged in the form of such minimal photoactive prebiotic kernel systems and later in the process of evolution these photoactive prebiotic kernel systems would have produced fatty acids and covered themselves with fatty acid envelopes to become the minimal cells of the Fatty Acid World. Specifically, we model self-assembling of photoactive prebiotic systems with observed quantum entanglement phenomena. We address the idea that quantum entanglement was important in the first stages of origins of life and evolution of the biospheres because simultaneously excite two prebiotic kernels in the system by appearance of two additional quantum entangled excited states, leading to faster growth and self-replication of minimal living cells. The quantum mechanically modelled possibility of synthesizing artificial self-reproducing quantum entangled prebiotic kernel systems and minimal cells also impacts the possibility of the most probable path of emergence of protocells on the Earth or elsewhere. We also examine the quantum entangled logic gates discovered in the modelled systems composed of two prebiotic kernels. Such logic gates may have application in the destruction of cancer cells or becoming building blocks of new forms of artificial cells including magnetically active ones.Keywords Photosynthetic prebiotic kernel Á Quantum self-assembly of prebiotic kernel Á Quantum entangled molecular orbitals Á Photosynthesis in prebiotic kernels Á Quantum entangled photosynthesis Á Photosynthetic minimal cell Á Electron density transfer Á Electron spin density transfer Á Quantum entanglement in systems composed of two prebiotic kernels Á Molecular quantum entangled logical gates

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“…The active components of artificial minimal cells that are in the process of being synthesized at Los Alamos National Laboratory (LANL) [1][2][3][4][5][6][7] in the USA in collaboration with the Center for Fundamental Living Technology (FLinT) at the University of Southern Denmark (SDU) are only a few nanometers in size. The LANL research project has been supported by the USA Department of Energy under Contract No.…”

Section: Introductionmentioning

confidence: 99%

Molecular Spintronics Control of Photosynthesis in Artificial Cell

Tamulis¹,

Grigalavicius²

2013

Jnl of Comp & Theo Nano

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Quantum density functional theory studied photosynthetic system consists of photoelectron donor neutral radical molecule (5-(4-(1-hydroxyethyl)phenyl)pentanoic acid (1), a precursor of fatty acid (pFA, 2-oxo-2-phenylethyl ester) molecule and water molecules. The system include an explicitly simulated aqueous environment consisting of some 155 atoms and is up to about 2.3 nm in diameter. The quantum mechanical based electron correlation interactions are the source of the weak hydrogen and Van der Waals chemical bonds that are critical to the behavior of this system. Polar water molecules increase the strength of these bonds and thus play a central role in the self assembly and functioning of the systems studied. The distances between the separated neutral radical, precursor of the fatty acid, and water molecules are comparable to Van der Waals and hydrogen bonding radii. As a result, these nonlinear quantum interactions compress the overall molecular system resulting in a smaller gap between the HOMO and LUMO electron energy levels that in turn allows enhanced tunneling of photoexcited electrons from the sensitizer molecule (1) to the pFA. Electron spin density transfer rates in the intense absorption states were calculated and visualized in neutral radicals supramolecule (1). The metabolism involves magnetically controlled photoexcitation of an electron in these neutral radical supramolecule which possess stable or oriented spin. The main quantum mechanical research result of this paper is that the non-conventional system which were proposed include the use of molecular spintronics logic gate to control growth and division of artificial living cell. The excited electron is used to cleave a waste organic molecule resulting in the formation of the desired product.

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Photorelease of Primary Aliphatic and Aromatic Amines by Visible-Light-Induced Electron Transfer

Cited by 51 publications

References 45 publications

Phototriggered DNA Phosphoramidate Ligation in a Tandem 5′-Amine Deprotection/3′-Imidazole Activated Phosphate Coupling Reaction

Phototriggered DNA Phosphoramidate Ligation in a Tandem 5′-Amine Deprotection/3′-Imidazole Activated Phosphate Coupling Reaction

Quantum entanglement in photoactive prebiotic systems

Molecular Spintronics Control of Photosynthesis in Artificial Cell

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