210
ISSN 0030-400X, Optics and Spectroscopy, 2016, Vol. 121, No. 2, pp. 210–219. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.A. Oleinikov, K.E. Mochalov, D.O. Solovyeva, A.A. Chistyakov, E.P. Lukashev, I.R. Nabiev, 2016, published in Optika i Spektroskopiya, 2016, Vol. 121,
No. 2, pp. 227–237.
The Effect of Silver Nanoparticles on the Photocycle
of Bacteriorhodopsin of Purple Membranes
of Halobacterium salinarum
V. A. Oleinikov
a,b
, K. E. Mochalov
a,b
, D. O. Solovyeva
a,b
, A. A. Chistyakov
a,b
,
E. P. Lukashev
c
, and I. R. Nabiev
b,d
a
Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences, Moscow, 117997 Russia
b
National Research Nuclear University, Moscow Engineering Physics Institute, Moscow, 115409 Russia
c
Moscow State University, Moscow, 119991 Russia
d
University of Reims Champagne-Ardenne, Reims, 51100 France
e-mail: voleinik@mail.ru
Received February 24, 2016
Abstract—The effect of silver nanoparticles (AgNPs) that are adsorbed on the surface of the purple mem-
branes of Halobacterium salinarium bacteria on the optical properties and functional peculiarities of the light-
sensitive protein bacteriorhodopsin (BR) has been demonstrated for the first time. Two mechanisms of the
effect of AgNPs on the protein photocycle have been demonstrated using Raman scattering, giant Raman
scattering, flash photolysis, and atomic force microscopy. It has been shown that the nanoparticles in the
immediate spatial vicinity of BR fix its photocycle at the stage where it was at the moment of interaction with
the nanoparticles. At greater distances, which reach three radii of an AgNPs, they have a weaker effect on BR,
under which it retains the ability to be involved in the photocycle, however, has its parameters significantly
changed. Thus, in the case of wild-type BR the photocycle accelerates and for the BR-D96N mutant it
becomes slower. The data that are obtained could be of significance for creation of such optoelectronic hybrid
systems with BR, where the parameters of its photocycle can be controlled using NPs. The results of the study
may also be used in the field of nanobioengineering research, which is directed to creation of unique materials
with controlled properties for recording and storage of information, energy transformation, and identification
and characterization of trace amounts of analytes.
DOI: 10.1134/S0030400X1608018X
INTRODUCTION
The resonance properties of nanoparticles (NPs)
are actively used in modern sensor technologies for
identification and investigation of the properties of
biological objects [1]. One of the most promising
directions in the development of these technologies is
the use of giant Raman spectroscopy (GRS) for selec-
tive detection and investigation of properties of single
bacteria, viruses, and living cells [2–4]. One of the
most popular systems that enhance Raman scattering
(RS) is conventionally represented by sols of metal
NPs. The enhancement of RS of the substance under
study occurs in these systems due to its adsorption on
the surface of NPs aggregates or due to formation of
these aggregates on the surface of a spatially extended
object such as bacteria. The Raman signal itself
increases due to the enhancement of an electromag-
netic field near the aggregates of metal NPs. The use
of NPs of noble metals is preferable, since the frequen-
cies of the surface plasmon resonance of spherical NPs
are within the optical range. In particular, the reso-
nance wavelength of spherical silver nanoparticles
(AgNPs) is approximately 400 nm, while that of gold
nanoparticles (AuNPs) is 550 nm. The position of the
peak of the plasmon resonance is shifted to the long-
wave region upon aggregation of NPs and/or change
in their shape [5].
Moreover, nanoparticles are used for modulation
of the function of light-sensitive proteins [6], e.g., bac-
teriorhodopsin (BR). The possibility to tune the
parameters of the resonance of NPs by changing their
shape, size, and degree of aggregation makes it possi-
ble to make hybrid nanosystems with resonance
energy transfer that are based on conjugates of NPs
and biological molecules. Examples of resonance
interactions with biomolecules can be both plasmon
interactions in a system of MeNPs and biomolecules
and interaction with excitons in semiconductor NPs,
quantum dots (QDs). In particular, the use of semi-
conductor NPs in these systems makes it possible to
broaden the spectral range of the natural protein func-
tion, proton transfer, due to the energy transfer from a
CONDENSED-MATTER
SPECTROSCOPY