Chemische Strategien für den Aufbau molekularer Logikelemente zur Addition und Subtraktion

Pischel, Uwe

doi:10.1002/ange.200603990

Cited by 86 publications

(27 citation statements)

References 140 publications

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“…In recent years photoinduced energy and electron transfer (ET) have been extensively studied, with the potential development of molecular electronics, [1][2][3][4] solar cells, [5][6][7][8][9] and artificial photosynthesis [10][11][12][13][14][15][16] as long-term goals. This has led to the design of many donor-bridge-acceptor (D-B-A) systems, which enable systematic investigations of how the transfer processes are mediated by the bridging chromophore.…”

Section: Introductionmentioning

confidence: 99%

Temperature Dependence of Electronic Coupling through Oligo‐p‐phenyleneethynylene Bridges

Eng¹,

Mårtensson²,

Albinsson³

2008

Chemistry A European J

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A series of donor-bridge-acceptor (D-B-A) systems with varying donor-acceptor distances has been studied with respect to the temperature dependence of the triplet excitation energy transfer (TEET) rates. The donor and acceptor, zinc(II) and free-base porphyrin, respectively, were separated by oligo-p-phenyleneethynylene (OPE) bridges, where the number of phenyleneethynylene groups was varied between two and five, giving rise to edge-to-edge separations ranging between 12.7 and 33.4 A. The study was performed in 2-MTHF between room temperature and 80 K. It was found that the distance dependence was exponential, in line with the McConnell model, and the attenuation factor, beta, was temperature dependent. The experimentally determined temperature dependence of beta was evaluated by using a previously derived model for the conformational dependence of the electronic coupling based on results from extensive quantum chemical, DFT and time-dependent DFT (TD-DFT), calculations. Two regimes in the temperature interval could be identified: one high-temperature, low-viscosity regime, and one low-temperature, high-viscosity regime. In the first regime, the temperature dependence of beta was, according to the model, well described by a Boltzmann conformational distribution. In the latter, the molecular motions that govern the electronic coupling are slowed down to the same order of magnitude as the TEET rates. This, in effect, leads to a distortion of the conformational distribution. In the high-temperature regime the model could reproduce the temperature dependence of beta, and the extracted rotational barrier between two neighboring phenyl units of the bridge structure, E(i)=1.1 kJ mol(-1), was in line with previous experimental and theoretical studies. After inclusion of parameters that take the viscosity of the medium into account, successful modeling of the experimentally observed temperature dependence of the distance dependence was achieved over the whole temperature interval.

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Section: Introductionmentioning

confidence: 99%

Temperature Dependence of Electronic Coupling through Oligo‐p‐phenyleneethynylene Bridges

Eng¹,

Mårtensson²,

Albinsson³

2008

Chemistry A European J

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“…The recently developed concept of enzymatic logic gates, [1][2][3] which are a part of general research areas of biochemical [4][5][6] and chemical computing, [7][8][9] is aimed at controlling various processes and systems through logically processed biochemical signals. Information processing by biochemical reactions that perform Boolean logic operations has resulted in the design of various enzymatic logic gates (for example, AND, OR, XOR, INHIB, NOR).…”

Section: Introductionmentioning

confidence: 99%

Biomolecular Oxidative Damage Activated by Enzymatic Logic Systems: Biologically Inspired Approach

et al. 2009

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Systems that perform oxidative damage to biomolecules through catalytic cascades in the presence of iron-redox labile species were activated by enzymatic logic gates that process chemical input signals according to built-in logic operations. AND/OR enzymatic logic gates were composed of glucose oxidase (GOx) and GOx/esterase, respectively. The AND/OR logic functions of the enzyme gates were activated by application of glucose-oxygen and glucose-ethyl acetate input signals, respectively. The enzymatic logic gates, upon activation by specific patterns of the chemical input signals, produced acidic solutions and triggered release of redox labile iron species from a complex that is unstable under acidic conditions. This resulted in the activation of a catalytic cascade, which produced reactive oxygen species (ROS) and subsequently yielded oxidative damage in biomolecules. Functional integration of the enzyme-based logic systems with the catalytic redox cascade that performs damage in biomolecules on demand is a first step towards "smart" systems capable of programmed detection, identification, and neutralization of potential biohazards.

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“…Since these pioneering reports, a large number of molecular HA and HS has been described in the literature, and several of these studies were discussed in comprehensive reviews. [9,11] Until 2005, separate molecules were used to realize the functions of the HA and the HS, respectively, i.e., there was no report of a molecule capable of performing addition as well as subtraction (the functions of a so-called moleculator). Interestingly, the first molecule shown to do so was the well-known fluorescent pH-indicator fluorescein (5; see Scheme 1), in a report by Shanzer and co-workers.…”

Section: Advanced Logic Operations Through Functional Integration Andmentioning

confidence: 99%

Information Processing with Molecules—Quo Vadis?

et al. 2012

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2 Lead-In. Information processing at the molecular level is coming of age. Since the first molecular AND gate was proposed ca. 20 years ago, the molecular interpretation of binary logic has become vastly more sophisticated and complex. However, the field is also at a crossroads. While cleverly designed molecular building blocks are abundant, difficult questions remain. How can molecular components be flexibly assembled into larger circuits, and how can these components communicate with one another. The concept of all-photonic switching with photochromic supermolecules has shown some interesting potential and is discussed in this Review. Although the field of molecular logic was originally discussed mainly in terms of a technology that might compete with solid-state computers, potential applications have expanded to include clever molecular systems and materials for drug delivery, sensing, probing, encoding, and diagnostics.These upcoming trends, which are herein illustrated by selected examples, deserve general attention.

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Chemische Strategien für den Aufbau molekularer Logikelemente zur Addition und Subtraktion

Cited by 86 publications

References 140 publications

Temperature Dependence of Electronic Coupling through Oligo‐p‐phenyleneethynylene Bridges

Temperature Dependence of Electronic Coupling through Oligo‐p‐phenyleneethynylene Bridges

Biomolecular Oxidative Damage Activated by Enzymatic Logic Systems: Biologically Inspired Approach

Information Processing with Molecules—Quo Vadis?

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