Ab Initio Quantum Chemical Design of Supermolecule Logical Devices and Nano-Medicine Robots

A. Tamulis, Z. Rinkevicius*, V. Tamulis, J. Tamuliene

Ab Initio Quantum Chemical Design of Supermolecule Logical Devices and

Nano-Medicine Robots

Institute of Theoretical Physics and Astronomy, A. Gostauto 12, 2600 Vilnius, Lithuania

*Kaunas Technology University, Faculty of Fundamental Sciences, Kaunas 3000, Lithuania

The mechanism of the isomerization of the Disperse Orange 3 molecule per linear transition state is suggested and investigated. The results of light induced internal molecular motions in stilbene and DO3 molecules have been used for the design of light driven logically controlled molecular machines composed from photoactive organic molecules such as carbazole, 1,4-phenylenediamine, TeMePhDA, 4,5-dinitro-9-(dicyanomethylidene)-fluorene, TCNB, TCNQ, Dithieno[3,2-b:2',3'-d]thiophene (see Figure 1) and Ferocene (C10H10Fe) molecules joined with –CH=CH- or -N=N- bridges.

Figure 1. The geometry of light-driven OR logically controlled molecular machine optimized by DFT B3PW91/6-311G** model.

Designed molecular logically controlled machine possessing absorption transitions in visible and near-UV regions that might permit two variable light induced motions. Molecular logically controlled machines should be used for oriental diffusion and transportation various medicine and remedy to the tissues of living organisms.

It was designed nano-robot composed from light-driven DO3 molecule biliverdinesthat have two beneficial physiological roles: anti-oxidant activity and anti-HIV activity (see Figure 2).

Figure 2. Supermolecular light-driven nano-robot composed from DO3 and CuOEB possessing anti-oxidant activity possibility in the living organisms.

Molecular Implementation (MI) of carbon based two, three, four variable logic functions, summators of neuromolecular networks, cells of molecular cellular automata, molecular trigger - molecular logic devices and molecular devices for electronically genome regulation were designed based on results of semiempirical and ab initio HF, DFT quantum chemical calculations of the electron donors, electron insulators, electron acceptors and fullerene molecules [1-3]. Complete set of sixteen MIs of two variable logic functions (for example: OR, AND, Implication, Equivalence, Difference, etc.) was designed and also proposed using MIs of two variable molecular logic function initial basic sets: {OR, AND, Negation} or {NOR} and, or {NAND}. We have described in more detail the designed MIs of: a) two variable logic functions OR, NOR, AND, NAND (from fullerene molecules), Converse Unitary Negation-1, Converse Unitary Negation-0, Unitary Negation-1, Unitary Negation-0, "0" and "1" Matrix Constants; b) three variable logic functions AND, NAND, OR, NOR analogs; c) four variable logic functions OR, NOR, AND, NAND analogs. The electron hoping via the insulator bridges in the supermolecules: electron donor-bridge-electron acceptor phenomenon was investigated by using CIS-HF method and our made visualization software.

We are performing design of molecular logical devices based on planar electron donor and electron acceptor molecules, series of fullerene C60 substituted derivatives: C60CH2, C60C2H4, etc., electron donor-bridge-electron acceptor dyads and triads (see Figure 3). Design of new series of more correctly organic molecules based MIs of two variable logic functions: OR, NOR, AND, NAND, Converse Unitary Negation-1, Converse Unitary Negation-0, Unitary Negation-1, Unitary Negation-0, "0" and "1" Matrix Constants is based on geometry optimization procedure in ground and excited states.

Figure 3. AND or NAND gate designed from two electron donor fragments and two electron acceptor molecules.

Ab initio quantum chemical investigations of novel fullerene derivatives allowed to design new stable molecular logic devices. The outputs of the designed molecular logic devices should be linked the gene expression signaling pathways or regulatory circuits. These logic gates should be attached to nucleoproteins that interact with DNA and control transcription of DNA.

The derivative (NH2)CH-ErSc2N@C80-CH(NO2) shows magnetic activity calculated by Restricted Open Shell HF method using Watanabe basis set in doublet electronic state is because of redistribution of total atomic spin densities on central ErSc2N cluster. Therefore this single supermolecule can be used as light induced switch of magnetic field in the basic elements of classical and quantum computers. The bulk materials based on supermolecules (NH2)CH-Sc3N@C80-CH(NO2) and (NH2)CH-ErSc2N@C80-CH(NO2) might be used for electro-optical and magneto-optical switches and for information storage. The ErSc2N clusters should be in coherent states in low temperatures of supramoleculer layer designed from (NH2)CH-ErSc2N@C80-CH(NO2) derivatives.

Quantum chemical investigations of azafullerene dimer (NH2)CH-NC59-NC59-CH(NO2) motions during photo excitation introduced new type of light driven single molecular machines. This material in bulk sizes might be used for information storage devices.

Our designed photoactive molecules, which perform motions during excitation, were used for design of molecular triggers (Figure 4). For example, our investigated light excited aza-fullerene supermolecule (NH2)CH-NC59-NC59-CH(NO2) should move from one not-connected end of molecular wire to another end and transfer the photo-excited electron. During photo-excitation electron jump from electron-donor fragment NH2- to electro-acceptor fragment -NO2. This passed photoelectron should switch molecular trigger from position '0' to position '1'.

Figure 4. Molecular trigger based on (NH2)CH-NC59-NC59-CH(NO2) supermolecule and scheme of molecular dynamic memory composed from various molecular triggers and molecular wires network.

The different isomers of aza-fullerene supermolecules: (NH2)(CH3)C-NC59-NC59-CH(NO2), (NH2)CH-NC59-NC59-C(CH3)(NO2), (NH2)(CH3)C-NC59-NC59-C(CH3)(NO2), (NH2)(CH3-CH2)C-NC59-NC59-CH(NO2), (NH2)CH-NC59-NC59-C(CH3-CH2)(NO2), (NH2)(CH3-CH2)C-NC59-NC59-C(CH3-CH2)(NO2), etc. possesses the different absorption wavelengths for electron-donor fragment NH2- therefore it is possible to control switching of different molecular triggers by different wavelengths.

[1] A. Tamulis, E. Stumbrys, V. Tamulis and J. Tamuliene, "Quantum Mechanical Investigations of Photoactive Molecules, Supermolecules, Supramolecules and Design of Basic Elements Molecular Computers", in NATO ASI series, High Technology; Vol. 9, Ed. by F. Kajzar, V. M. Agranovich and C. Y.-C. Lee, Photoactive Organic Materials: Science and Applications, June 25-30, 1995, Avignon, France, Kluver Academic Publishers, Doderecht/Boston/London, p.p. 53-66 1996.

[2] A. Tamulis, V. Tamulis, "Design of Basic Elements of Molecular Computers Based on Quantum Chemical Investigations of Photoactive Organic Molecules", Proceedings of the SPIE Photonics WEST® Conference on Optoelectronic Integrated Circuits II, held in 24-30 January, 1998, San Jose Convention Center, San Jose, California, U.S.A., Volume 3290, p.p. 315-324.

[3] A. Tamulis, V. Tamulis and J. Tamuliene, Quantum Mechanical Design of Molecular Implementation of Two, Three and Four Variable Logic Functions for Electronically Genome Regulation, Viva Origino, 26, p.p. 127-146, 1998.