Ferredoxin:NADP + oxidoreductase in junction with CdSe/ZnS quantum dots: characteristics of an enzymatically active nanohybrid (original) (raw)
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Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2014
The development of new hybrid materials that can be integrated into current technologies is one of the most important challenges facing material scientists today. The purpose of this work is to review recent studies in one largely unexplored area of nanobiotechnology: the development of nano-bio hybrid materials that exploit Förster Resonance Energy Transfer (FRET) to enhance the functionalities of technologically promising photosynthetic biomaterials. One of very promising approaches is to employ semiconductor quantum dots having a broad absorption spectrum as nanoantennae coupled with the natural lightharvesting complexes of photosynthetic reaction centers. This system reveals great potential for the utilization of quantum dots in artificial photosynthetic devices. The second very useful functionality, which is discussed in this review, is the possibility to enhance the efficiency of the main biological function (proton pumping) of the protein bacteriorhodopsin using nonradiative energy transfer from quantum dots. Also recent studies revealed that FRET-based improvement of the biological function of bacteriorhodopsin in the presence of quantum dots allows for strong wavelength-dependent enhancement of the nonlinear refractive index of bacteriorhodopsin. These new hybrid bio-nanomaterials with exceptional light-harvesting and nonlinear properties will have numerous photonic applications employing their photochromic, energy transfer, and energy conversion properties.
Nanoscale Research Letters, 2015
Basic principles of structural and functional requirements of photosynthetic energy conversion in hierarchically organized machineries are reviewed. Blueprints of photosynthesis, the energetic basis of virtually all life on Earth, can serve the basis for constructing artificial light energy-converting molecular devices. In photosynthetic organisms, the conversion of light energy into chemical energy takes places in highly organized fine-tunable systems with structural and functional hierarchy. The incident photons are absorbed by light-harvesting complexes, which funnel the excitation energy into reaction centre (RC) protein complexes containing redox-active chlorophyll molecules; the primary charge separations in the RCs are followed by vectorial transport of charges (electrons and protons) in the photosynthetic membrane. RCs possess properties that make their use in solar energy-converting and integrated optoelectronic systems feasible. Therefore, there is a large interest in many laboratories and in the industry toward their use in molecular devices. RCs have been bound to different carrier matrices, with their photophysical and photochemical activities largely retained in the nano-systems and with electronic connection to conducting surfaces. We show examples of RCs bound to carbon-based materials (functionalized and nonfunctionalized single-and multiwalled carbon nanotubes), transitional metal oxides (ITO) and conducting polymers and porous silicon and characterize their photochemical activities. Recently, we adapted several physical and chemical methods for binding RCs to different nanomaterials. It is generally found that the P + (Q A Q B) − charge pair, which is formed after single saturating light excitation is stabilized after the attachment of the RCs to the nanostructures, which is followed by slow reorganization of the protein structure. Measuring the electric conductivity in a direct contact mode or in electrochemical cell indicates that there is an electronic interaction between the protein and the inorganic carrier matrices. This can be a basis of sensing element of bio-hybrid device for biosensor and/or optoelectronic applications.
Bio-nanohybrids of quantum dots and photoproteins facilitating strong nonradiative energy transfer
Nanoscale, 2013
Utilization of light is crucial for the life cycle of many organisms. Also, many organisms can create light by utilizing chemical energy emerged from biochemical reactions. Being the most important structural units of the organisms, proteins play a vital role in the formation of light in the form of bioluminescence. Such photoproteins have been isolated and identified for a long time; the exact mechanism of their bioluminescence is well established. Here we show a biomimetic approach to build a photoprotein based excitonic nanoassembly model system using colloidal quantum dots (QDs) for a new bioluminescent couple to be utilized in biotechnological and photonic applications. We concentrated on the formation mechanism of nanohybrids using a kinetic and thermodynamic approach. Finally we propose a biosensing scheme with an ON/OFF switch using the QD-GFP hybrid. The QD-GFP hybrid system promises strong exciton-exciton coupling between the protein and the quantum dot at a high efficiency level, possessing enhanced capabilities of light harvesting, which may bring new technological opportunities to mimic biophotonic events.
A biocompatible amine functionalized fluorescent carbon dots were developed and isolated for gram scale applications. Such carbogenic quantum dots can strongly conjugate over the surface of the chloroplast and due to that strong interaction the former can easily transfer electrons towards the latter by assistance of absorbed light or photons. An exceptionally high electron transfer from carbon dots to the chloroplast can directly effect the whole chain electron transfer pathway in a light reaction of photosynthesis, where electron carriers play an important role in modulating the system. As a result, carbon dots can promote photosynthesis by modulating the electron transfer process as they are capable of fastening the conversion of light energy to the electrical energy and finally to the chemical energy as assimilatory power (ATP and NADPH).
Biosensing and Probing of Intracellular Metabolic Pathways by NADH-Sensitive Quantum Dots
Angewandte Chemie-international Edition, 2009
The use of semiconductor quantum dots (QDs) as optical labels for biorecognition events and biocatalytic processes attracts growing interest. While numerous studies reported on the use of the QDs as fluorescent labels, applications of semiconductor QDs as optical probes of dynamic bioprocesses, such as enzymatic transformations, using fluorescence resonance energy transfer (FRET) or photoinduced electron transfer reactions are still scarce. The replication of DNA by polymerase or telomerization of a nucleic acid by telomerase were monitored by the incorporation of a dye into the replica/ telomers associated with QDs and the use of FRET as readout signal. The scission of duplex DNA linked to CdSe QDs by DNase and the hydrolytic cleavage of peptides bound to CdSe QDs were followed by FRET processes. Recently, the activities of tyrosinase and thrombin were analyzed by the tyrosinase-induced generation of quinone residues on amino acid or peptide capping layers associated with CdSe QDs. This resulted in electron-transfer quenching of the QDs. The subsequent hydrolytic cleavage of the peptide by thrombin removed the quencher and recovered the fluorescence of the QDs.
2021
Reaction centers (RCs) are the pivotal component of natural photosystems, converting solar energy into the potential difference between separated electrons and holes that is used to power much of biology. RCs from anoxygenic purple photosynthetic bacteria such as Rhodobacter sphaeroides only weakly absorb much of the visible region of the solar spectrum which limits their overall light-harvesting capacity. For in vitro applications such as bio-hybrid photodevices this deficiency can be addressed by effectively coupling RCs with synthetic lightharvesting materials. Here, we studied the time scale and efficiency of Förster resonance energy transfer (FRET) in a nanoconjugate assembled from a synthetic quantum dot (QD) antenna and a tailored RC engineered to be fluorescent. Time-correlated single photon counting spectroscopy of biohybrid conjugates enabled the direct determination of FRET from QDs to attached RCs on a time scale of 26.6 ± 0.1 ns and with a high efficiency of 0.75 ± 0.01.
Enhancement of Photosynthetic Productivity by Quantum Dots Application
Nonmagnetic and Magnetic Quantum Dots, 2018
The challenge of climate change promotes use of carbon neutral fuels. Biofuels are made via ixing carbon dioxide via photosynthesis which is ineicient. Light trapping pigments use restricted light wavelengths. A study using the microalga Botryococcus braunii (which produces bio-oil), the bacterium Rhodobacter sphaeroides (which produces hydrogen), and the cyanobacterium Arthrospira platensis (for bulk biomass) showed that photosynthetic productivity was increased by up to 2.5-fold by upconverting unused wavelengths of sunlight via using quantum dots. For large scale commercial energy processes, a 100fold cost reduction was calculated as the break-even point for adoption of classical QD technology into large scale photobioreactors (PBRs). As a potential alternative, zinc sulide nanoparticles (NPs) were made using waste H 2 S derived from another process that precipitates metals from mine wastewaters. Biogenic ZnS NPs behaved identically to ZnS quantum dots with absorbance and emission maxima of 290 nm (UVB, which is mostly absorbed by the atmosphere) and 410 nm, respectively; the optimal wavelength for chlorophyll a is 430 nm. By using a low concentration of citrate (10 mM) during ZnS synthesis, the excitation wavelength was redshifted to 315 nm (into the UVA, 85% of which reaches the earth's surface) with an emission peak of 425 nm, i.e., appropriate for photosynthesis. The potential for use in large scale photobioreactors is discussed in the light of current PBR designs, with respect to the need for durable UV-transmiting materials in appropriate QD delivery systems.
Journal of the American Chemical Society, 2022
A semiartificial photosynthesis approach that utilizes enzymes for solar fuel production relies on efficient photosensitizers that should match the enzyme activity and enable long-term stability. Polymer dots (Pdots) are biocompatible photosensitizers that are stable at pH 7 and have a readily modifiable surface morphology. Therefore, Pdots can be considered potential photosensitizers to drive such enzyme-based systems for solar fuel formation. This work introduces and unveils in detail the interaction within the biohybrid assembly composed of binary Pdots and the HydA1 [FeFe]-hydrogenase from Chlamydomonas reinhardtii. The direct attachment of hydrogenase on the surface of toroid-shaped Pdots was confirmed by agarose gel electrophoresis, cryogenic transmission electron microscopy (Cryo-TEM), and cryogenic electron tomography (Cryo-ET). Ultrafast transient spectroscopic techniques were used to characterize photoinduced excitation and dissociation into charges within Pdots. The study reveals that implementation of a donor−acceptor architecture for heterojunction Pdots leads to efficient subpicosecond charge separation and thus enhances hydrogen evolution (88 460 μmol H2 •g H2ase −1 •h −1). Adsorption of [FeFe]-hydrogenase onto Pdots resulted in a stable biohybrid assembly, where hydrogen production persisted for days, reaching a TON of 37 500 ± 1290 in the presence of a redox mediator. This work represents an example of a homogeneous biohybrid system combining polymer nanoparticles and an enzyme. Detailed spectroscopic studies provide a mechanistic understanding of light harvesting, charge separation, and transport studied, which is essential for building semiartificial photosynthetic systems with efficiencies beyond natural and artificial systems.