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wileyonlinelibrary.com Adv. Mater. 2011, 23, 4261–4264
Netta Hendler, Bogdan Belgorodsky, Elad D. Mentovich, Michael Gozin,*
and Shachar Richter*
Efficient Separation of Dyes by Mucin: Toward Bioinspired
White-Luminescent Devices
N. Hendler, B. Belgorodsky, E. D. Mentovich, Dr. M. Gozin,
Dr. S. Richter
School of Chemistry
Faculty of Exact Sciences
Tel Aviv University
Ramat Aviv, Tel Aviv 69998, Israel
E-mail: cogozin@mgchem.tau.ac.il; srichter@post.tau.ac.il
N. Hendler, E. D. Mentovich, S. Richter
University Center for Nanoscience and Nanotechnology
Tel Aviv University
Ramat Aviv, Tel Aviv 69998, Israel
DOI: 10.1002/adma.201100529
The production of organic white-light-emitting devices is one of
the main technological and scientific challenges in the field of
optoelectronics
[1–4]
because the formation of such a broad emis-
sion spectrum with the use of a single dye is difficult to accom-
plish.
[5,6]
In practice, the emission of white light is achieved by
the use of a mixture of the three primary dyes, which emit red
(R), green (G), and blue (B) light.
[7]
However, as a result of non-
radiative interactions between very close color elements, such as
Förster resonance energy transfer (FRET), an undesirable shift
in the emission spectrum is often observed, which prevents the
achievement of white-light emission.
[8]
The two main approaches to resolving this problem are the
construction of multilayers of dyes in which each separate layer
consists of a single type of dye and the synthesis of a separating
material in which the different emitting compounds can be
mixed while separated by some minimal distance at which the
dye interactions are negligible (matrix–filler materials).
[9]
Most of the common matrix materials consist of inorganic
compounds that can be polymerized into thin films in which
the different dyes, usually molecular dyes or polymeric species,
can be incorporated.
[10]
While these systems are the leading
candidates for the preparation of flexible, processable, and inex-
pensive devices,
[3,11]
the fabrication process of such systems is
greatly affected by environmental parameters such as humidity,
temperature, and concentration.
[11]
Thus, control of the com-
plex with its multi-ingredient phase diagram remains very chal-
lenging and the search continues for simpler alternative matrix
materials.
[12,13]
Here we suggest exploiting nature’s ability to form many
types of stable and controllable host–guest systems
[14–16]
for the
construction of a new type of robust matrix material and use the
material for the construction of protein luminescent films (PLUF)
and devices. This simple methodology involves the extraordinary
capabilities of certain types of hydrophilic proteins to host hydro-
phobic compounds without affecting their properties.
[17,18]
We
show that simple blending of the guest dyes in a protein bioma-
trix enables the formation of a variety of PLUFs, all excited by
a common single wavelength, emitting at wavelengths ranging
from pure R, G, and B to white. Furthermore, although most of
the common dyes used for emitting devices are not water-soluble,
the design of our new complexes enables the production of water-
soluble materials under ambient and “green” conditions.
In general, host–guest interactions play a crucial role in many
vital biochemical processes,
[17]
including transport, solubility,
catalysis, sensing, self-assembly, distribution ratios in immis-
cible solvents, and drug–receptor interactions. It is no coinci-
dence that these interactions are the basis of many biological
systems, whose efficiencies will long continue to surpass that of
synthetic systems by orders of magnitude.
In practice, proteins are the most suitable candidates for our
goals because of their large host–guest capacities and the types
of interaction and the range of guest compounds that can be
incorporated in the matrix. The latter are the most common
biomolecules that play important roles in the interactions,
storage, and transport of various exogenic materials. Among
the important groups of proteins that are well known for their
properties of binding and solubilization of hydrophobic lig-
ands is the family of mucins.
[19]
These glycoproteins are major
components in the mucus that coats the surfaces of cells that
line the respiratory, digestive, and urogenital tracts.
[20]
Mucin
proteins constitute more than 80% of the organic compo-
nents of mucus and serve as a first line of defense and delivery
mediator common to both the gastrointestinal and respiratory
systems.
[21]
We have previously shown that bovine submaxillary mucin
(BSM) protein is capable of binding and solubilizing water-
insoluble nanomaterials in physiological solution.
[19]
Here we
utilize the extraordinary uptake properties of BSM to engineer
light-emitting solutions and PLUFs. The structure of BSM is
shown in Figure 1. This biodendrimer compound is highly
glycosylated, composed of 80% carbohydrates. Its oligosac-
charide chains consist of 5–15 monomers, show moderate
branching, and are attached to the protein core by O-glycosidic
bonds to the hydroxyl side chains of serine and threonine and
arranged in a “bottle-brush” configuration around the pro-
tein core. The monomeric BSM units (MW ≈ 170 kDa) are
connected via disulfide-rich domains and form a dendritic
structure.
The fluorescent BSM solutions and PLUFs were prepared
using several types of commercially available hydrophobic light-
emitting dye molecules as fillers (Figure 1). Physical separa-
tion between the dyes was achieved by separate incorporation
of each type of dye in the BSM host followed by mixing an