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DOI: 10.1002/asia.201100114

Dispersible Shortened Boron Nitride Nanotubes with Improved MoleculeLoading Capacity

Chunyi Zhi,*[a] Nobutaka Hanagata,[b] Yoshio Bando,[a] and Dmitri Golberg[a]
tubes. The shortened boronnitride
nanotubes were found to possess good
solubility in water and many organic
solvents. Further experiments demon-

Abstract: The oxidation process of

boron nitride nanotubes was thoroughly investigated, and a slow oxidation
characteristic was clearly revealed.
Subsequently, the controllable oxidation process was utilized to break the
sturdy structure of the boron nitride
nanotubes to fabricate shortened nano-

Keywords: boron nanotubes

nitrides oxidation solubility

Introduction
For various applications of nanotubes, especially bioapplications,[14] processibility and dispersibility of nanotubes are of
primary importance. Therefore, the development of easy
and effective functionalization methods for soluble nanotubes is essential for extending their use. Moreover, in some
cases, the long fibrous structure of nanotubes may cause
problems including fibrous-structure-induced toxicity and
difficulties with cell uptake, for example.[58] Therefore,
shortened nanotubes may possess advantages, such as better
processibility and dispersibility, improved biocompatibility,
and easier cell uptake, over pristine as-prepared tubes,
which can be more suitable for bioapplications. Shortening
nanotubes has been an important research topic for years
and various methods have been developed.[911] For example,
sonication is the usual physical method for shortening nanotubes, however, it is not so effective due to the sturdy structure of nanotubes. Chemical methods, such as oxidation are

[a] Dr. C. Zhi, Prof. Y. Bando, Prof. D. Golberg

International Center for Materials Nanoarchitectonics (MANA)
National Institute for Materials Science (NIMS)
Namiki 1-1, Tsukuba, Ibaraki 305-0044 (Japan)
Fax: (+ 81) 29-8516280
E-mail: Zhi.Chunyi@nims.go.jp
[b] Prof. N. Hanagata
Nanotechnology Innovation Center
National Institute for Materials Science (NIMS)
Namiki 1-1, Tsukuba, Ibaraki 305-0044 (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201100114.

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strated remarkably improved moleculeloading capacity of the shortened

boron nitride nanotubes. These dispersible shortened boron nitride nanotubes might have the potential to be
developed as effective delivery systems
for various molecules, which may find
applications in bio-related fields.

effective for breaking up nanotubes, but it is difficult to control the oxidation process to obtain the desired structure.[12]
Boron nitride nanotubes (BNNTs), which have similar
structures to carbon nanotubes (CNTs), are interesting due
to their super structural stability and antioxidation ability,[13]
great mechanical properties,[1416] and high thermal conductivity.[1719] Moreover, good biocompatibility has been recently revealed for BNNTs[20, 21] and it has been proven that
BNNTs may interact with various molecules, including conjugated polymers,[22, 23] proteins,[24, 25] DNA,[26, 27] and dyes.[28, 29]
These characteristics make BNNTs a promising material for
various applications.
In this paper, we demonstrate an easy method for the fabrication of shortened BNNTs, which possess good solubility
in many conventional reagents and remarkably improved
molecule-loading capacity. The approach of our method is
shown in Figure 1. The slow oxidation process of BNNTs
was investigated thoroughly and it was utilized to break the
stubborn structure of BNNTs. Subsequently, soluble shortened BNNTs were fabricated successfully by sonicating oxidized BNNTs. Dramatically improved dispersibility and remarkably improved molecule-loading capacity of the shortened BNNTs were demonstrated.

Results and Discussion

The BNNTs used in our experiments were synthesized by a
chemical vapor deposition method using boron and metal
oxide as precursors. The detailed growth procedure was reported elsewhere.[30, 31] The as-grown BNNTs were purified

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Chem. Asian J. 2011, 6, 2530 2535

oxidation started and the BNNTs began to be converted

into B2O3. The weight losstime dependence curve revealed that the oxidation started at 830 min, and from
1020 min the weight started to decrease due to completion of oxidation and subsequent evaporation of B2O3.
This demonstrates a very slow oxidation process at
1000 8C: oxidation of 2.356 mg BNNTs takes around
Figure 1. A schematic diagram of the fabrication procedure of dispersible
shortened BNNTs and using them for molecule loading.

at high temperatures up to approximately 1900 8C under the

protection of argon gas to remove impurities. Purified
BNNTs are pure white. Scanning electron microscopy
(SEM) observation revealed that our BNNTs possess diameters of around 50 nm, and the length can be up to tens of
micrometers, as shown in Figure 2.
The antioxidation ability of BNNTs was studied by thermogravimetric analysis (TGA), as shown in Figure 3a.[32] In
a typical experimental run, it was revealed that at around
820 8C, the weight started to increase, which indicates that

Figure 3. Temperature-dependent TGA curve and time-dependent TGA

curve (inset).

Figure 2. SEM images of as-grown BNNTs after purification.

Chem. Asian J. 2011, 6, 2530 2535

190 min (it should be noted that this time duration depends
on the amount of BNNTs used and the contact area between air and the BNNTs, however, a characteristic of slow
oxidation of BNNTs below 1000 8C is clearly revealed).
The slow oxidation makes it possible to break the stubborn structure of the BNNTs in a controlled manner. Although it was revealed by TGA that oxidation happens at
820 8C, detailed studies indicate that it is actually very slow
and that 5 h oxidation at 820 8C doesnt make any obvious
defects on the BNNTs. As shown in Figure 4a and b, only
very occasionally, broken parts can be found on some
BNNTs, and it is not clear whether these parts are due to
high-temperature oxidation or not because pristine BNNTs
may also contain some defects. Upon 5 h oxidation at
1000 8C, BNNTs become very defective, and almost all of
the walls of BNNTs were not integrated any more. Walls
become thinner, and holes appear. Some tubes were almost
broken with twisted BN fringes at the broken area, as
shown in Figure 4c to f. It should be noted that at 1100 8C,
the oxidation of BNNTs becomes much faster, in less than
2 h, 1 g of BNNTs can be oxidized into B2O3 completely.
The appearance of B O bonds was monitored by Fourier
transform infrared (FTIR) spectroscopy (Figure 5), which
revealed that B O bonds appear in large amounts at 950 8C.
Therefore, it is suggested that for controllable oxidation of
BNNTs, 9501000 8C is a suitable temperature range. It is
proposed that perfect BNNTs may be very difficult to oxidize. The oxidation at 9501000 8C starts from defect sites
and/or ends of the BNNTs. N vacancies appear and B sites

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are saturated by oxygen, as indicated in Figure 1, which results in the defective structure of BNNTs.
Broken, oxidized BNNTs make it possible to shorten the
BNNTs effectively by sonication. The BNNTs oxidized at
1000 8C for 5 h were sonicated by a tip-type sonicator for
5 h. Pristine unoxidized BNNTs were also treated under the
same conditions for comparison. As shown in Figure 6a and
b, after sonication, although much shorter than the original

Figure 4. TEM images of oxidized BNNTs before shortening by sonication. a) and b) BNNTs oxidized at 820 8C for 5 h; no obvious oxidationinduced defects can be observed. c) to f) Upon oxidation at 1000 8C for
5 h, the BNNT become very defective with broken walls, holes, twisted
fringes, and so forth.

Figure 5. FTIR spectra of oxidized BNNTs at different temperatures.

Characteristic peaks of B2O3 at 640 and 2260 cm 1 appear in the oxidized
BNNT samples from 950 8C.

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Figure 6. a) and b) TEM images of pristine BNNTs after 5 h sonication:

they possess a length of more than 5 mm. c) and d) TEM images of shortened BNNTs by sonicating oxidized BNNTs; they are much shorter than
pristine BNNTs.

as-grown BNNTs, most of the unoxidized BNNTs still have

a length of more than 5 mm. As a comparison, most shortened oxidized BNNTs possess a length of around 1 mm, and
some of them were shortened to hundreds of nanometers. In
addition, it is believed that at new ends of shortened
BNNTs, B sites are saturated by O, which means the shortened BNNTs were also functionalized. Evidence for this is
that the shortened BNNTs can be well dispersed in most
common organic solvents, such as alcohol and N,N- dimethylformamide (DMF), as shown in Figure 7. Moreover,
compared with hydrophobic pristine BNNTs, the shortened
BNNTs can be well dispersed in water. Clearly, the appearance of oxygen on the surfaces and ends of BNNTs, as well
as the shortened morphology play important roles in the improvement of dispersibility.
As mentioned above, BNNTs can interact with various
molecules, which make it possible to utilize BNNTs as molecule carriers. It is thought that the dispersible shortened
BNNTs may possess an improved molecule-loading capacity,
which is a very important factor for developing effective de-

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Chem. Asian J. 2011, 6, 2530 2535

Shortened Boron Nitride Nanotubes

Figure 7. Solubility comparison of pristine BNNTs and functionalized

shortened BNNTs: I and III are pristine BNNTs in water and alcohol, respectively; II and IV are shortened oxidized BNNTs in water and alcohol, respectively.

livery systems. To demonstrate this, polyvinylpyrrolidone

(PVP) and DNA sodium salt, which was reported to interact
with BNNTs previously,[2628, 33] were used to interact with
pristine BNNTs and dispersible shortened BNNTs, respectively. TGA was used to analyze the amount of PVP and
DNA finally absorbed on the BNNTs, as shown in Figure 8a.
Since BNNTs possess superb antioxidation ability, the
weight loss of the molecule-loaded shortened BNNTs is believed to be mainly due to degradation of organic materials.
As summarized in Figure 8b, for PVP, compared with
around 5.0 % weight loss of pristine BNNTs, the weight loss
reaches 12.7 % for shortened BNNTs. In the case of DNA
sodium salt, a 9.2 % weight loss was obtained for shortened
BNNTs instead of the 5.7 % weight loss observed for pristine BNNTs. (The ratio of DNA sodium salt absorbed is actually more than the weight loss obtained because under
these conditions, pure DNA sodium salt has a weight loss of
73 %; see the Supporting Information). The shortened
BNNTs possess a hole-rich structure and more ends than
pristine BNNTs, which provides more chances for molecules
to enter the tubes. Therefore, molecules can be held on/in
shortened BNNTs instead of solely located on the surface of
long pristine BNNTs. Moreover, the better dispersibility of
shortened BNNTs increases the chances of BNNTmolecule
interactions. These factors finally result in a larger loading
capacity. Our assumption is supported by TEM observation,
as shown in Figure 9. In most cases, the end of the BNNTs
is filled with amorphous material, and amorphous material
can also be observed in some whole short BNNTs. Because
the shortened BNNTs possess more ends, the improved molecule-loading capacity is reasonable. It should be noted that
that shortened nanostructure may also provide easier cell
uptake and improved biocompatibility than materials with
long fibrous structures,[7] therefore, we propose that the dispersible shortened BNNTs may be developed to be various
delivery systems for different molecules.

Chem. Asian J. 2011, 6, 2530 2535

Figure 8. a) TGA analysis of molecule-loaded dispersible shortened

BNNTs and pristine BNNTs; b) loading capacity comparison of PVP and
DNA sodium salt with pristine and dispersible shortened BNNTs, respectively.

Figure 9. a) and b) TEM images of PVP-loaded shortened BNNTs; c)

and d) TEM images of DNA sodium salt loaded shortened BNNTs.

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FULL PAPERS
Conclusions
In conclusion, dispersible shortened BNNTs were fabricated
by developing a simple process. Our process and fabricated
material possess advantages as follows: 1) the fabrication
process utilizes slow oxidation characteristic of BNNTs,
which can be easily controlled and scaled up; 2) compared
with nondispersible pristine BNNTs, the shortened BNNTs
possess good solubility in various solvents, including water;
3) the molecule-loading capacity of the dispersible shortened BNNTs was remarkably improved compared with pristine BNNTs; 4) the dispersible shortened BNNTs may possess improved biocompatibility and easier cell uptake than
those with long tubes. Based on these advantages, it is believed that the dispersible shortened BNNTs may be developed to be effective delivery systems for a variety of molecules, which may promote research into the application of
BNNTs and nanomedicine. Related work is underway.

Experimental Section
TGA Analysis of BNNTs Oxidation
In a typical experimental run, the BNNTs (2.356 mg) were put in an alumina crucible for TGA measurement. The temperature was raised to
1000 8C and kept at 1000 8C for 2 h. Because the oxidation of the BNNTs
might be slow, a slow temperature increase rate of 1 8C min 1 was used.
For the weight loss analysis of PVP and the DNA sodium salt hybrid of
pristine/dispersible shortened BNNTs, the materials were put in a aluminum crucible and heated up to 600 8C at a rate of 1 8C min 1 and kept at
600 8C for 2 h.
TGA experiments were performed with a Rigaku Thermo Plus TG8120.
Oxidation of BNNTs
The BNNTs (1 g) were put in an alumina crucible and oxidized at 600,
820, 900, 950, and 1000 8C for 5 h, respectively. The oxidation of BNNTs
at 1100 8C was found to be very fast: in 2 h, 1 gram of BNNTs can be oxidized completely. After oxidation, the BNNTs were washed with boiled
water to remove possible B2O3 on their surface. Structures of oxidized
BNNTs were investigated by TEM, and surface bonding was investigated
by FTIR.
Shortening BNNTs by Sonication
The oxidized and washed BNNTs were put into a Teflon bottle and
enough amount of alcohol was added. A ultrasonic generator (Model
US-300T) produced by Nissei Electric Co. Ltd. with a power of around
300 W was used for sonication for 5 h. The BNNTs were filtered off after
sonication.
Molecule Loading
For molecule loading with PVP, pristine BNNTs (10 mg) or dispersible
shortened BNNTs (20 mg) were dispersed in alcohol and mixed with
PVP (20 mg; Wako company; average molecular weight: 3100 to 3900),
which was proved to interact with BNNTs strongly and improve their dispersiblity in solvents. After 1 h sonication and 10 h magnetic stirring, the
BNNTs were removed by centrifugation and washed. To remove PVP,
which is not absorbed on BNNTs tightly, the centrifugation washing processes were repeated three times.
For molecule loading with DNA, pristine BNNTs (20 mg) or dispersible
shortened BNNTs (20 mg) were mixed with water (20 mL) followed by
1 h sonication and 10 h stirring. Then DNA sodium salt (50 mg; deoxyribonucleic acid sodium salt from salmon sperm produced by Wako company) was added and the solution was heated up to 90 8C and stirred for

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5 h. Then the BNNTs were removed by centrifugation and washed. To

remove DNA sodium salt, which is not absorbed on BNNTs tightly, the
centrifugation washing processes were repeated three times.
Characterization
A scanning electron microscope (JEOL SM67F) was used to characterize
the BNNTs. The microstructures were analyzed using a JEOL-3000F
high-resolution field-emission transmission electron microscope operated
at 300 kV. FTIR spectra were collected by using a PerkinElmer FTIR
spectrometer with a laser wavelength of 1024 nm.

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Received: February 6, 2011
Published online: June 15, 2011

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