Nano Energy (2015) 11, 654–661

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/nanoenergy

RAPID COMMUNICATION

Heterogeneous bacteriorhodopsin/gold
nanoparticle stacks as a photovoltaic system
Zhibin Guo, Dawei Liang, Siyuan Rao, Yan Xiangn

Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, Beijing
Key Laboratory of Bio-inspired Energy Materials and Devices, School of Chemistry and Environment,
Beihang University, Beijing 100191, PR China

Received 19 August 2014; received in revised form 16 October 2014; accepted 11 November 2014
Available online 8 December 2014

KEYWORDS Abstract
Bacteriorhodopsin; To mimic the stack structure of granum, for the first time we demonstrate bacteriorhodopsin (bR)/
Stack system; gold nanoparticles (AuNPs) heterogeneous multilayers to perform as a novel photovoltaic stack
Photocycle; system with improved photoelectric performance. Upon a cooperative control of the diameter of
Photoelectric AuNPs and the stacking layers, the photocurrent can be effectively regulated to reach about
performance
350 nA cm ! 2. The possible mechanism for enhanced photocurrent recorded in our system is
revealed by analyzing the flash kinetics of photocycle intermediates M412, O640, and J600 of bR
layers, which are accelerated under proper AuNPs in this stacking structure. A bypass photocycle
model of bR photocycle from M412 to B570 state is proposed and supported by tested accumulation of
M412 and O640 intermediate during the bR photocycle process. Interestingly, with this stack system,
the input flickering light can be effectively modulated into regular photoelectric signals that are
well controlled under different flickering frequency and proton concentration gradient. Based on
above results, this system potentially serves as solar energy converter to power nano-devices.
& 2014 Elsevier Ltd. All rights reserved.

Introduction bacteriorhodopsin (bR) system in Halobacterium halobium.

Photosynthetic systems in nature are green and efficient
energy technologies for solar energy conversion over millions
of years. It includes two main different photosynthetic systems
[1], well-developed chloroplast system in green plant and
n
Corresponding author.
E-mail address: xiangy@buaa.edu.cn (Y. Xiang).
Green plants, meanwhile, exhibit a process for light-to-
charge conversion that provides a useful model for using solar
energy efficiently. Granum [2], the core organ in photosynth-
esis, consists of a stack of " 10–100 thylakoids containing
pigments and electrons acceptors, which provide a larger
surface area to capture solar radiation efficiently. Upon light
stimulated the antenna pigment molecules, electrons are
excited and transferred to accomplish photoelectric conversion
process (Figure 1a). Recent investigation has reported that this

http://dx.doi.org/10.1016/j.nanoen.2014.11.026
2211-2855/& 2014 Elsevier Ltd. All rights reserved.
Heterogeneous bacteriorhodopsin/gold nanoparticle stacks as a photovoltaic system 655

Figure 1 Design and mimic of the stacking structure of granum. a, Diagram of chloroplast in green plant. The granum contained
disc-like photoreceptors. Evolution has frequently used chloroplast to complete the photosynthetic process in green plant. After
light is captured through the antenna pigment molecules, electrons are excited and transferred. b, Scheme of the bR/AuNPs
heterogeneous structure. The bR and Au nanoparticles were designed to deposit alternatively on the AAO nanochanels. After light
illumination, the protons were transferred from CP side to EC side directionally. Owing to the surface plasmonic effect of AuNPs, the
photocycle path was shortened to pump more protons in a fixed time. The pore size of the AAO nanochanels is 5976 nm and keeps
constant in all experiments mentioned in this article. c, Top view of the stacking structure from the bR side and the side view of bR/
AuNPs stacks. bR layers densely packed at the surface of AAO nanochannel. In our bR/AuNPs stack, the bR layers are densely covered
the surface of AAO nanochannels to maintain the proton gradient between two half cells.
656
stack structure is benefit for improving the photoelectric
performance that the photoelectric response enhanced about
20 times by constructing TiO2 nanosheets with graphene as a
stack system [3]. But in artificial biological system, this stack
structure was not reconstructed and attracted more attention.
bR, the other photosynthetic units, is the only protein
component of the purple membrane (PM), a two-dimensional
crystal lattice in the cytoplasmic membrane of Halobactrium
halobium [4,5]. With contribution of lipid around bR molecule,
it forms trimer structure with an extreme chemical and
thermal stability. It functions as a light-driven proton pump,
which makes this protein as a strategic molecule with potential
applications in biotechnology [6–9]. The incorporation of bR
into photoelectric field leads to applications such as artificial
retina [10], light batteries[11], solar conversion units [12,13],
and photo switching component [14]. As a bionano component,
bR is a potential candidate for integrating within nano-devices,
which can effectively used as a solar energy converter[15].
However, a limitation arises from its poor energy conversion
efficiency compared to semiconducting metal oxides[16,17].
There are various strategies introduced to improve the photo-
electric performance of bR-based system. As one of effective
method, bR multilayers were demonstrated through layer-by-
layer assembly process[18–20] and electrodepostion[21], for
example, in poly-L-lysine (PLL)/bacteriorhodopsin film, the
peak photocurrent generated from PLL/bR-PM film enhances
with increase of the PLL/bR-PM bilayers[20]. Doping modifica-
tion has been involved by introducing the Au and Ag nanopar-
ticles with an excellent surface plasmon field effect into bR
solution, the photocurrent can be greatly improved [13,22],
but for solid-state bR layers, how to improve the photocurrent
substantially is not explored.
Here, to mimic the stack structure of granum, for the first
time we present bR/AuNPs heterogeneous multilayers to
reproduce this stack structure and serve as a photovoltaic
stack system (Figure 1b), where solid bR layers build as a
stack of photon acceptors, and AuNPs layers enhance the
photocurrent due to its native surface plasmon field effect
could accelerate the photocycle of bR molecule.
Experimental section
Growth, purification, and sample preparation of bR
suspension
bR was isolated and purified from Halobacterium halobium
strain R1M1 according to the standard procedure described
by Oesterhelt and Stoeckenius [23], then washed at least
three times with ultrapure water (Milli-Q, " 18 MΩ cm ! 1)
and finally suspended in it. The absorption of A280 nm/A568 nm
was below 1.6, indicating that the bR product was in good
quality. The concentration of bR suspension used in the
experiment is about 1.2 mg/ml. The suspensions were adjus-
ted by using 0.1 M NaOH to pH 9.0.
Preparation of bR/AuNPs stacks and pristine bR
stacks
The bR/AuNPs stack structures on anodic aluminum oxide
(AAO) nanochannel were obtained by the electropho-
retic sedimentation method. Firstly, AuNPs were coated the
Z. Guo et al.
surface of AAO nanochannels by ion sputtering. Then, the bR
solution (1.2 mg/ml) was electrodeposited on it by electro-
deposition (20 Vcm ! 1 5 min). When an aqueous solution
containing bR has a pH in the range of 5–12, the bR will
orient and deposit when placed between conductive plates
and a voltage is applied. The electric field between the
plates causes the cytoplasmic side (the more negatively
charged side) to electrophoretically move and deposit on
the AuNPs coated AAO substrate in the positive electrode. For
the bR-contained PM patches is about 2 μm, which is larger
than the pore size of AAO nanochannel that is about 50 nm.
So the bR layers were covered the surface of AAO nanochan-
nel effectively. This method is simple to perform, and the
orientation of the bR can be effectively controlled [24]. A
space formed between two ITO electrodes to push them
approximately 1 mm apart with an AAO covering the positive
indium tin oxide (ITO) electrode. Using a microsyringe, bR
suspension (pH=9) with concentrations 5 mg ml ! 1 was
injected into the gap between the two electrodes and then
3–6 V of electric potential was applied across the electrodes.
Finally, the bR/AuNPs stack structure was formed by alter-
nately sputtering the AuNPs and electrodepositing bR layers
several times. The stack multilayers were dried under a
relative humidity of 50–60%. The control samples (the pristine
bR stacks) were prepared based on the above electrophoretic
sedimentation method under the same bR concentration, pH
value, and applied potential without the procedure of AuNPs
sputtering. To repeat the electrophoretic sedimentation
process, the pristine bR stacks (multilayers) were formed.
The stack multilayers were dried under a relative humidity of
50–60%. Each sample obtained in this work was stable and
maintained activity for a long period of time (at least six
months).
Material characterization method
The morphology of the composite membranes was recorded
on a scanning electron microscope (SEM) with energy dis-
persive spectroscopy (EDS) detector (Camscan 3400, Oxford
Instruments) at 20 kV accelerating voltage. To view the cross
section of membrane, all samples were ruptured in liquid
nitrogen, followed by the sputtering of platinum on the cross
section and surface of the as prepared samples. The X-ray
diffraction analysis for the diameter of gold nanoparticles was
performed with a Philips diffractometer (Philips X‘ pert)
equipped with a Cu-Kα source (40 KV and 30 mA).
Photocurrent measurement
Details can be found in the Supporting Information (Figure
S1). As depicted in the Figure S1b, the custom-designed
photoelectrochemical cell was introduced. Modified from
the electrochemical cell designed by Mostafa A. El-Sayed
[14] and Horn[19], two teflon half electrochemical cells
(20 mm # 20 mm # 2 mm with D =5 mm hole in the center)
were separated by the alumina nanochannel arrays with bR/
AuNPs stacks or pristine bR stacks. The electrodes were two
pieces of ITO glass (12 mm # 25 mm). Each half-cell was
filled with 1.5 ml of the electrolyte solution of Hydrochloric
acid at different concentration (10, 1, 0.1, and 0.01 mM) to
Heterogeneous bacteriorhodopsin/gold nanoparticle stacks as a photovoltaic system 657

construct a proton concentration gradient between two
half cells.
The photocurrent measurement was carried out by using
a continuous-wavelength (CW) broadband light as the
excitation sources. The light was introduced from a Tung-
sten Lamp (PLS-SXE250), through an optical filter and
modulated with a photochopper (Model SR540 Stanford
Research System, Inc.). The current signal generated by
our devices was collected by an electrochemical work-
station (Par 2273, Princeton Instruments) by chronoampero-
metry method under bias voltage of 0.1 V added between
positive and negative electrodes. A visible light power
meter (Model 842-PE) was used to detect the incident
excitation energy. Dark incident photocurrent was collected
before addition of bR multilayers to eliminate any photo
artifacts. This dark photocurrent density (0.1 nA cm ! 2) was
subtracted from the induced photocurrent values for bR
multilayers herein. Each test was repeated five times to
obtain the average current value at different external
stimulus.
Transient absorption kinetics study of the
intermediate states
The transient absorption of bR intermediate states (M412,
O640, J600) was performed by Laser Flash Photolysis Spectro-
meter LP920-KS (Edinburgh Instruments). The excitation
light was 570 nm. To study the kinetics of M412, O640, J600,
the halogen lamp was introduced to detect the transient
absorption of 412 nm, 640 nm, and 600 nm. The decay time
of M412, O640, J600 were calculated by exponential fitting.
Results and discussion
In order to build the stack structure of granum illustrated in
Figure 1a, AAO nanochannel arrays is introduced. According to
our recent results [25], modified AAO nanochannel can effec-
tively regulate the photoelectric signal. Moreover, in our
previous study, bR/AAO nanosystem was demonstrated, in which
AAO nanochannels served not only a suitable substrate to

Figure 2 Photocurrent recorded and regulated in bR/AuNPs stack system. a, Photocurrent recorded based on the bR/AuNPs stack
(Inset is the enlarged spike photoelectric signal). b, Photocurrent recorded with sole bR layer (without AuNPs coated). The
photocurrent was enhanced about 46% after modified with AuNPs layer. c, The AuNPs coated different sides of bR layers to influence
the photocurrent. AuNPs modified the CP side of bR layer and can get a higher photocurrent, which is own to the plasmonic field
effect of AuNPs mainly influenced the reprotonation process occurred in the CP side. d, The stacking layer cooperates with the
proper size of AuNPs to enhance the amplitude of photocurrent. The optimized parameters are found to be two stacking layers and
22 nm of AuNPs in diameter.
658 Z. Guo et al.

support bR layers, but also cooperate with bR layers to regulate
the photocurrent and the optimal size of AAO nanochannel was
determined (about 59 nm). Then AuNPs layer and bR layers
were alternatively deposited over the AAO nanochannel array.
The surface and cross-section morphologies of the as-prepared
bR/AuNPs multilayers layers were examined by environmental
scanning electron microscopy (ESEM). As shown in Figure S2a,
the top view of AAO nanochannels after gold nanoparticles
modified (inset is the high magnification). The gold nanoparti-
cles are deposited over the surface and into the inner side of
AAO nanochannels. As observed on top view the stack structure
from bR side (Figure 1c), bR/AuNPs stacks are densely packed at
the surface of AAO nanochannels. The EDX shows the peaks
attributable to S, P, Ca, and Mg atoms that are the character-
istic elements of protein were appeared after bR multilayers
formed (Figure S2c). The similar densely packed structure is
also observed in the cross-sectional SEM images (Figure 1c and
Figure S2d–f). The typical stacks of 2, 4, and 8 are preformed
with a clear interface between the layers. Based on above ESEM
results, the bR layer combines with AuNPs layer densely and the
alternately bR/NPs multilayers are formed.
After the stacks were prepared, the photoelectric per-
formance was illustrated. To our knowledge, bR molecules
exhibit a differential response upon continuous-wavelength
irradiation[26,27], which the photocurrent is proportional to
the change in the illumination level. The light induced release
by bR of proton onto the extracellular (EC) side of the PM and
the subsequent uptake of proton from the cytoplasmic (CP)
side is apparently directional[14].Thus the different polarity of
photoelectric signal about 350 nA cm ! 2 is recorded with onset
and cessation of stimulated light in this stack system com-
pared with the pristine bR layers (Figs. 2a and b). The AuNPs
layer in our photovoltaic system can effectively enhance the
photocurrent about 46% in amplitude.
In the proton pump process of bR molecule, the CP side
related to the reprotonation process and EC side related to the
protonation process. In our system, the photocurrent is
enhanced about 56% when AuNPs contact with CP side of bR
layers (Figure 2c). This observation possible results from the
plasmonic field effect of AuNPs that mainly influenced the
reprotonation rate of shiff base proton pump process occurred
in the CP side in the bR photo cycle process [22,28,29].

Figure 3 The transition absorption kinetics of bR-based samples. a, The optical density (OD) of intermediate M412 and O640 in the
photocycle of bR/AuNPs two layers and pristine bR two layers. The stimulated light was 570 nm. The OD of M412 and O640 were detected at
412 nm and 640 nm respectively. b, O640 to M412 ratio in the bR/AuNPs and pristine bR range from one to three layers. Mechanism
illustration of bR/AuNPs stack system: c, The photocycle path of bR, with several intermediate state in the whole photocycle process. After
coated with AuNPs, the photocycle was shortened from M412 state straightforward to B state owning to the plasmonic field effect of AuNPs.
d, A bypass photocycle model: the equivalent level diagram of the photochemical cycle in these stacks.
Heterogeneous bacteriorhodopsin/gold nanoparticle stacks as a photovoltaic system 659

In order to study interdependence of gold size distribution with distance increased. And also the inner resistance of
and number of stack layers to solid bR layers, the multilayers bR/ AuNPs is increased with the stack layers, which leads to
of bR/AuNPs heterogeneous stacks is built. It is found that the decrease in the amplitude of the photocurrent.
diameter of AuNPs cooperate with stack layer can effectively To clearly illustrate the enhanced photocurrent recorded in
regulated the photocurrent (Figure 2d), which the optimal this bR/AuNPs heterogeneous stack system, the O640, M412, and
parameters is about 22 nm and two layers respectively. This O640 to M412 ratio are further analyzed. As depicted in the
phenomenon may results from the surface plasmon field of Figure 3a, in the case of bR/AuNPs layers and pristine bR
AuNPs affected by particle size distribution and distance from layers, the main intermediates M412 and O640 of bR photocycle
the nanoparticle center. With the stack layer increased (above are detected in the full spectrum of transition absorption
two layers), the photocurrent is decreased owing to the kinetics. Over the same period of time, the optical density
increased resistance of whole stack structure (Figure S3). (OD) of M412 in bR/AuNPs stacks is enhanced while the OD of
The mechanism of the plasmonic field effect of AuNPs to O640 is suppressed in bR/AuNPs stacks than it in the pristine bR
solid bR layers could be chemical enhanced effect. Through layers. This illustrated that bR/AuNPs stack likely benefits the
transient absorption kinetics study, the mainly distinguished accumulation of M412 that related to the proton release and
intermediate states (O640, M412, J600) can be detected in this uptake process, which is identified in Figure 3b. The O640 to
system that means the solid bR layers keep bioactivity and M412 ratio in both bR/AuNPs systems is obvious lower than in
complete the traditional photocycle pathway (As shown in pristine bR systems range from one to three layers which
Figure 3c,I) [30,31]. However, the decay time is distin- suggested the AuNPs layer did inhabit the generation and
guished upon the different layer number of stacks (Table 1). accumulation of O640. Based on the above results, a bypass
When the stack number is 2, both the O640, M412, and J600 photocycle model is proposed as in Figure 3c,d. When a
states are accelerated, thus the photocycle speed of the bR continuous wavelength stimulated (350–800 nm) is introduced,
layers accelerated (Table 1). We can record the much higher AuNPs is pumped to the excited state and then emit light about
photocurrent with two heterogenous stacks that may 520 nm. With absorption of this light, the photocycle of bR
ascribe to the above reason. With increasing of the stack layers are taken place from B570 state to the J600 state, and
layers, the plasmonic field of gold nanoparticles decayed then pass to the M412 state. In our stimulated light source, the
blue light is contained which directly affects the bR to
accelerate the decay of its M412 intermediate just formed
Table 1 The decay time of M412, O640, J600 intermedi- [32]. That means the light activated the M412 to an excited
ate in bR photocycle. state Me [33], which decays to B state in a shorter time through
pathway II to complete a photocycle (As described in Figure 3c ).
Pure 1 2 3 4 5 The results shown in Figs. 3a and3b are the strong evidence
bRn stack# stacks stacks stacks stacks to support our proposed bypass photocyle model (Figure 3c,
d). With the addition of AuNP layers, photocycle pathway of
M412 81 29 3 42 97 130 partial bR molecule will directly decays from M412 state to B
(ms) state without through O640 state.
O640 31 29 17 39 43 55 Then above mechanism can be summarized as follows: upon
(μs) light illumination, with the AuNPs is introduced, some bR
J600 36 37 24 31 40 41 molecules are pumped to the excited state Me, then decay
(μs) to B570 state through a bypass way. Some bR molecules can
n
Pure bR: 1 solid-state bR layer without AuNPs. complete the traditional photocycle pathway with faster
#
1 stack: 1 solid-state bR layer combined with 1AuNPs speed which result from the plasmonic field of AuNPs speeds
layer up the reprotonation rate of schiff base proton pump process
in the bR photosynthetic system.

Figure 4 The amplitude of photocurrent controlled by the frequency of stimulated light. a, The amplitude of the photocurrent
depends on the frequency of the stimulated light. b, The system is also tested with continuously changing flickering light stimuli.
Continuous photoelectric signals are obtained below 80 Hz.
660
Moreover, as a photovoltaic system, the peak photocurrent
is effectively regulated in our system by the frequency of
stimulated light that is the photocurrent initially increases
with a flickering frequency increase; but it then quickly
decreased at a higher frequency (Figure 4a). With this system,
the input flickering light is converted to regular photoelectric
signal. The spike signal recorded is similar to that reported in
ZnO-based system [34], however, our heterogeneous stack
system is novel protein based and easy to fabricate with a
stable signal. Furthermore, bR/AuNPs stack can instanta-
neously respond to a continuously changing flickering light
below 80 Hz with a distinguishable photocurrent and out-
standing reproducibility (Figure 4b). Such a biological system,
as an example, would potential spark experimental efforts to
explore more complex smart system with real time responds.
Conclusion
In summary, here we successfully built the granum-like
heterogeneous bR/AuNPs photovoltaic stack system. The
photocurrent recorded in this stack system reaches to about
350 nA cm ! 2 under optimal conditions. More importantly, a
novel bypass photocycle model for bR/AuNPs with improved
photoelectric performance is proposed and strongly supported
by tested accumulation of M412 and O640 intermediate during
the bR photocycle process. Therefore, our studies bring
forward a new method to fabricate bR-based device with
excellent photoelectric performance and clear mechanism.
Acknowledgments
This work was financially supported by the National Research
Fund for Fundamental Key Projects (2011CB935700), the
National Natural Science Foundation of China (51422301,
U1137602, 21373022, 21073010, 21103201), Beijing Nova
Program (Z131109000413008), Program for New Century Excel-
lent Talents in University, and Fundamental Research Funds for
the Central Universities and Innovation Foundation of BUAA for
PhD Graduates (YWF-14-YJSY-048). We thank Prof. K.S. Hu
(Institute of Biophysics, Chinese Academy of Sciences), Prof. J.
Zhai, Prof. D.L. Chen (Graduate University of Chinese Academy
of Sciences), Dr. L.P. Wen (Institute of Chemistry, Chinese
Academy of Sciences) for beneficial discussions.
Appendix A. Supporting information
Supplementary data associated with this article can be
found in the online version at http://dx.doi.org/10.1016/
j.nanoen.2014.11.026.
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Zhibin Guo is a PhD candidate in the School
of Chemistry and Environment, Beihang
University. He received his B.E. in Polymer
Science and Engineering from Beijing Insti-
tute of Graphic Communication in 2007. He
joined Prof. Xiang's group in 2008 to pursue
his PhD career. His current research focuses
on biohybrid photoelectric materials and
devices.
Heterogeneous bacteriorhodopsin/gold nanoparticle stacks as a photovoltaic system 661

Dr. Dawei Liang received his BE and ME in
Environmental Engineering from Harbin Insti-
tute of Technology in 2000 and 2002, and his
PhD in Environmental Engineering from the
University of Hong Kong in 2007. He was a
postdoc research fellow at National University
of Singapore from 2007 to 2009. He joined
Beihang University in 2009 and now he is an
associate Professor in School of Chemistry and
Environment, Beihang University. His research
focuses on the environmental biotechnology, especially on bioelectro-
chemical systems for wastewater treatment, energy conversion, and
storage.
Dr. Yan Xiang received her PhD in Physical
Chemistry from Sichuan University, China in
2001. She joined Beihang University in 2001
and spent one year on green catalysis as a
postdoc in Carnegie Mellon University, USA.
Now she is the full professor of Materials
Chemistry at School of Chemistry & Envir-
onment, Beihang University. Her research
focuses on biohybrid materials and devices
for energy conversion.

Siyuan Rao is currently a PhD candidate at

School of Chemistry and Environment, Bei-
hang University (BUAA), China. She received
her BS degree (2010) from Beihang Univer-
sity and joined Prof. Xiang‘s group to pursue
her PhD career. Her current scientific inter-
ests are focused on the design and fabrica-
tion of bio-hybrid photoelectric systems and
bio-component integrated sensors.