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INIZIO_TESTO_DA_INDICIZZARE

RESEARCH PROGRAM

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Scientific and education field classification
International Patent Classification
  • CHEMISTRY; METALLURGY
  • PHYSICS
    • MEASURING (counting G06M); TESTING
      • INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (separating components of materials in general B01D, B01J, B03, B07; apparatus fully provided for in a single other subclass, see the relevant subclass e.g. B01L; measuring or testing processes other than immunoassay, involving enzymes or micro-organisms C12M, C12Q; investigation of foundation soil in situ E02D1/00; sensing humidity changes for compensating measurements of other variables or for compensating readings of instruments for variations in humidity, see G01D or the relevant subclass for the variable measured; testing or determining the properties of structures G01M; measuring or investigating electric or magnetic properties of materials G01R; systems or methods in general, using reception or emission of radiowaves or other waves and based on propagation effects, e.g. Doppler effect, propagation time, direction of propagation, G01S; determining sensivity, graininess, or density of photographic materials G03C5/02; testing component parts of nuclear reactors G21C17/00; [N: controlling or regulating non-electric variables G05D; measuring degree of ionisation of ionised gases, i.e. plasma H05H1/00A; testing electrographic developer properties G03G15/08H6])
Geographical classification
Bibliografia
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Keywords
ELECTRON TRANSFER, HYBRID SYSTEMS, METALLOPROTEINS, ULTRAFAST PUMP-PROBE SPECTROSCOPY, SCANNING PROBE MICROSCOPY, EXCITED STATE DYNAMICS, PROTEIN COLLECTIVE MODES, SINGLE MOLECULE, SERS

Excited state charge-transfer dynamics and electron transfer in metalloprotein-based hybrid systems: an ultrafast pump-probe and nanoscopic investigation.

Università degli Studi della Tuscia
Abstract
The project is devoted to study the excited state charge-transfer dynamics and electron transfer in metalloprotein-based hybrid systems by means of an innovative approach mainly involving the combined use of Scanning Probe Microscopies (SMPs) and femtosecond pump-probe spectroscopy with the aim of a better understanding the electron transfer (ET) processes through metalloproteins and across the interface between molecules and metal electrodes representing one of the major challenges in nano-biotechnology. This integrated approach enables to characterize and directly observe the ET through molecules and between molecule and metallic surface down to single-molecule levels and gives access to the dynamics of electronic and vibrational levels. In particular, SPMs will provide information on the tunnelling mechanism in charge transfer and conductive properties of hybrid systems. On the other hand, femtosecond pump-probe spectroscopy will enable the characterization of the excited state population and nuclear dynamics together with a description of the coupling among the protein’s electronic levels, the ET pathway and the occurrence of possible protein collective motions after a light-driven ET. The study will be completed by steady state optical spectroscopies (including Resonant Raman-RR- and Surface-enhanced Raman Spectroscopy-SERS) and topological characterization (by Atomic Force Spectroscopy) of the hybrid systems.
The investigations will be co-ordinately carried on >>>

Principal Investigator
Salvatore Cannistraro Università degli Studi della TUSCIA
Research Objectives
Recently, a new class of nano-biosensors and optoelectronic nanodevices, based on metalloproteins in intimate contact with a metallic substrate, has been proposed [1-6]. Metalloproteins in hybrid systems can function as biological recognition element, as electronic transducer with low dissipation, or as element for converting light into an electric signal [5]. However, device function rests fundamentally on charge transfer through protein, whose biological functionality has to be preserved, and across the interface between molecules and electrodes. Thus, the understanding and description of charge transfer mechanisms, protein conductivity and electron transfer (ET) excited state dynamics in both isolated and hybrid-system integrated metalloproteins is one of the major objectives in nano-biotechnology.
In this frame, the project is devoted to a detailed study of the excited state charge-transfer dynamics and of the ET in metalloproteins both isolated and bound to gold surfaces. Mainly two different types of tools will be used for these investigations: (i) scanning probe microscopies (SPMs), such as Scanning Tunneling Microscopy (STM) and Spectroscopy (STS) and Conductive Atomic Force Microscopy (CAFM) [7-10]; (ii) femtosecond pump-probe spectroscopy [11,12]. The combination of these two complementary approaches, together with the joined use of steady state optical spectroscopies (including Resonant Raman-RR, Surface-enhanced Raman Spectroscopy-SERS), will enable a key >>>

Timescale
24 months
National and international background
Integrating biological building blocks with electrical transducers into synthetic materials and devices allows to combine natural biological functions, such as binding, catalysis, recognition and electron transfer (ET), with the processing power of modern microelectronics for the realization of biosensors, devices for driving biotransformations, solar cells, and eventually biocomputers [47,48]. Moreover, by considering that most biological reactions occur at surfaces and interfaces, exploring mutual interaction between individual biomolecules and various surfaces is of fundamental importance [1,49,50]. In this framework, redox metalloproteins have gained considerable interest in nanoscale technology because they function as mobile electron carriers in a wide variety of biological systems and for their very efficient inherent ET (thanks to the presence of a redox center). Indeed, the peculiarity of ET processes mediated by metalloproteins is that they occur over long distances, in a very fast (typical ET rate constants for biological processes lie around 10^2–10^3 s^-1), directional way at the level of the single electron [51,52]. Furthermore, some metalloproteins show very peculiar optical properties well suited to induce an ET by visible irradiation [35]. Such characteristics, besides the possibility of gating redox activity and their nanoscale dimensions, make them a good candidate for incorporation in hybrid submicrometer-sized systems [16,53-56]. Thus, the understanding >>>