Unidirectional rotation of micromotors on water powered by pH-controlled disassembly of chiral molecular crystals.

Biological and synthetic molecular motors, fueled by various physical and chemical means, can perform asymmetric linear and rotary motions that are inherently related to their asymmetric shapes. Here, we describe silver-organic micro-complexes of random shapes that exhibit macroscopic unidirectional rotation on water surface through the asymmetric release of cinchonine or cinchonidine chiral molecules from their crystallites asymmetrically adsorbed on the complex surfaces. Computational modeling indicates that the motor rotation is driven by a pH-controlled asymmetric jet-like Coulombic ejection of chiral molecules upon their protonation in water. The motor is capable of towing very large cargo, and its rotation can be accelerated by adding reducing agents to the water.

Fabrication of Electronic Junctions between Oriented Multilayers of Photosystem I and the Electrodes of Optoelectronic Solid-State Devices.

The efficient optoelectronic properties of photosynthetic proteins were explored in the quest for the fabrication of novel solid biohybrid devices. As most optoelectronic devices function in a dry environment, an attempt was made to fabricate an efficient electronic junction by covalent binding of photosynthetic reaction center proteins to metals, transparent semiconductor polymers, and solid semiconductors that function in a dry environment. The primary stages of photosynthesis take place in nanometric-size protein-chlorophyll complexes. Such is photosystem I (PSI), which generates a photovoltage of 1 V. The isolated PSI generates an absorbed light-energy conversion efficiency of ∼47% (∼23% solar energy) and internal quantum efficiency of ∼100%. The robust cyanobacterial PSI was used in the fabrication of solid-state optoelectronic devices by forming oriented multilayers from genetically engineered cysteine mutants between metal and transparent conducting semiconductor electrodes. Current-voltage measurements of the cells generated diode- and photodiode-like responses in the dark and the light, respectively. The cells were stable for many months in a dry environment. The generation of photocurrent and Voc indicated the formation of good electronic coupling between PSI and the electrodes, which can serve in the fabrication of solid-state biohybrid optoelectronic devices.

Chemical Tagging of Membrane Proteins Enables Oriented Binding on Solid Surfaces.

In biological systems, membrane proteins play major roles in energy conversion, transport, sensing, and signal transduction. Of special interest are the photosynthetic reaction centers involved in the initial process of light energy conversion to electrical and chemical energies. The oriented binding of membrane proteins to solid surfaces is important for biotechnological applications. In some cases, novel properties are generated as a result of the interaction between proteins and solid surfaces. We developed a novel approach for the oriented tagging of membrane proteins. In this unique process, bifunctional molecules are used to chemically tag the exposed surfaces of membrane proteins at selected sides of membrane vesicles. The isolated tagged membrane proteins were self-assembled on solid surfaces, leading to the fabrication of dens-oriented layers on metal and glass surfaces, as seen from the atomic force microscopy (AFM) images. In this work, we used chromatophores and membrane vesicles containing protein chlorophyll complexes for the isolation of the bacterial reaction center and photosystem I, from photosynthetic bacteria and cyanobacteria, respectively. The oriented layers, which were fabricated on metal surfaces, were functional and generated light-induced photovoltage that was measured by the Kalvin probe apparatus. The polarity of the photovoltage depended on the orientation of proteins in the layers. Other membrane proteins can be tagged by the same method. However, we preferred the use of reaction centers because their orientation can be easily detected by the polarity of their photovoltages.

Spatial modulation of light transmission through a single microcavity by coupling of photosynthetic complex excitations to surface plasmons.

Molecule-plasmon interactions have been shown to have a definite role in light propagation through optical microcavities due to strong coupling between molecular excitations and surface plasmons. This coupling can lead to macroscopic extended coherent states exhibiting increment in temporal and spatial coherency and a large Rabi splitting. Here, we demonstrate spatial modulation of light transmission through a single microcavity patterned on a free-standing Au film, strongly coupled to one of the most efficient energy transfer photosynthetic proteins in nature, photosystem I. Here we observe a clear correlation between the appearance of spatial modulation of light and molecular photon absorption, accompanied by a 13-fold enhancement in light transmission and the emergence of a distinct electromagnetic standing wave pattern in the cavity. This study provides the path for engineering various types of bio-photonic devices based on the vast diversity of biological molecules in nature.

Spin selectivity in electron transfer in photosystem I.

Photosystem I (PSI) is one of the most studied electron transfer (ET) systems in nature; it is found in plants, algae, and bacteria. The effect of the system structure and its electronic properties on the electron transfer rate and yield was investigated for years in details. In this work we show that not only those system properties affect the ET efficiency, but also the electrons' spin. Using a newly developed spintronic device and a technique which enables control over the orientation of the PSI monolayer relative to the device (silver) surface, it was possible to evaluate the degree and direction of the spin polarization in ET in PSI. We find high-spin selectivity throughout the entire ET path and establish that the spins of the electrons being transferred are aligned parallel to their momenta. The spin selectivity peaks at 300 K and vanishes at temperatures below about 150 K. A mechanism is suggested in which the chiral structure of the protein complex plays an important role in determining the high-spin selectivity and its temperature dependence. Our observation of high light induced spin dependent ET in PSI introduces the possibility that spin may play an important role in ET in biology.

Photocurrent of a single photosynthetic protein.

Photosynthesis is used by plants, algae and bacteria to convert solar energy into stable chemical energy. The initial stages of this process--where light is absorbed and energy and electrons are transferred--are mediated by reaction centres composed of chlorophyll and carotenoid complexes. It has been previously shown that single small molecules can be used as functional components in electric and optoelectronic circuits, but it has proved difficult to control and probe individual molecules for photovoltaic and photoelectrochemical applications. Here, we show that the photocurrent generated by a single photosynthetic protein-photosystem I-can be measured using a scanning near-field optical microscope set-up. One side of the protein is anchored to a gold surface that acts as an electrode, and the other is contacted by a gold-covered glass tip. The tip functions as both counter electrode and light source. A photocurrent of ∼10 pA is recorded from the covalently bound single-protein junctions, which is in agreement with the internal electron transfer times of photosystem I.

Tuning the critical temperature of cuprate superconductor films with self-assembled organic layers.

Control over the T(c) value of high-T(c) superconductors by self-assembled monolayers is demonstrated (T(c) = critical temperature). Molecular control was achieved by adsorption of polar molecules on the superconductor surface (see scheme) that change its carrier concentration through charge transport or light-induced polarization.

Broad band enhancement of light absorption in photosystem I by metal nanoparticle antennas.

The photosystem I (PS I) protein is one of nature's most efficient light harvesting complexes and exhibits outstanding optoelectronic properties. Here we demonstrate how metal nanoparticles which act as artificial antennas can enhance the light absorption of the protein. This hybrid system shows an increase in light absorption and of circular dichroism over the entire absorption band of the protein rather than at the specific plasmon resonance wavelength of spherical metal nanoparticles (NPs). This is explained by broad-resonant and nonresonant field enhancements caused by metal NP aggregates, by the high dielectric constant of the metal, and by NP-PS I-NP antenna junctions which effectively enhance light absorption in the PS I.

On-chip functionalization of carbon nanotubes with photosystem I.

We optoelectronically functionalize carbon nanotubes (CNTs) with the photosynthetic reaction center photosystem I (PSI) according to three different on-chip chemical routes. The PSI is bound to the CNTs via covalent, hydrogen, or electrostatic bonds. Our approach allows the electrical contact of single PSI-CNT hybrid systems where the orientation of the PSI with respect to the CNTs depends on the binding mechanism. Our data are consistent with the interpretation that if the PSI is anchored with its internal electron transport path perpendicular to CNTs, the optical excitation of the PSI leads to an enhanced photoconductance of the hybrid system.

The optoelectronic properties of a photosystem I-carbon nanotube hybrid system.

The photoconductance properties of photosystem I (PSI) covalently bound to carbon nanotubes (CNTs) are measured. We demonstrate that the PSI forms active electronic junctions with the CNTs, enabling control of the CNTs' photoconductance by the PSI. In order to electrically contact the photoactive proteins, a cysteine mutant is generated at one end of the PSI by genetic engineering. The CNTs are covalently bound to this reactive group using carbodiimide chemistry. We detect an enhanced photoconductance signal of the hybrid material at photon wavelengths resonant to the absorption maxima of the PSI compared to non-resonant wavelengths. The measurements prove that it is feasible to integrate photosynthetic proteins into optoelectronic circuits at the nanoscale.

Picosecond electron transfer from photosynthetic reaction center protein to GaAs.

An extremely fast electron transfer through an electronically coupled junction between covalently bound oriented photosynthetic reaction center protein photosystem I (PS I) and n-GaAs was measured by time-resolved photoluminescence. It was found that the n-GaAs band edge luminescence intensity increased by a factor of 2, and the fast exponential decay constant was increased by a factor of 2.6 following the PS I self-assembly. We attribute this to picosecond electron transfer from the PS I to the n-GaAs surface states.

Hybrid structures composed of photosynthetic system and metal nanoparticles: plasmon enhancement effect.

The efficiency of chemical energy production of a photosynthetic system can be strongly enhanced in the presence of metal nanoparticles. Two competing effects contribute to the photosystem efficiency: plasmon enhancement of photon fields inside the light-absorbing chlorophyll molecules and energy transfer from chlorophylls to metal nanoparticles. The first effect can lead to strong enhancement of light absorption by the chlorophylls, whereas the second can somewhat reduce the quantum yield of the system. This paper describes one concrete example of hybrid photosystem that incorporates a photosynthetic reaction center bound to gold and silver nanocrystals. The calculated rate of production of excited electrons inside the reaction center is strongly increased due to plasmon resonance and fast electron-hole separation. In phototransport experiments with photosynthetic reaction centers, the plasma resonance can enhance the photocurrent response. The enhancement mechanism described here can be utilized in energy-conversion devices and sensors.