Chem Soc Rev: Tutorial Review
Chem Soc Rev: Tutorial Review
Chem Soc Rev: Tutorial Review
Anti-Stokes shift luminescence is a special optical process, which converts long-wavelength excitation
to short-wavelength emission. This unique ability is especially helpful for bio-applications, because the
longer-wavelength light source, usually referring to near infrared light, has a larger penetration depth
offering a longer working distance for in vivo applications. The anti-Stokes shift luminescence signal can
also be distinguished from the auto-fluorescence of biological tissues, thus reducing background
interference during bioimaging. Herein, we summarize recent advances in anti-Stokes shift luminescent
Received 31st May 2016 materials, including lanthanide and triplet–triplet-annihilation-based upconversion nanomaterials, and
DOI: 10.1039/c6cs00415f newly improved hot-band absorption-based luminescent materials. We focus on the synthetic strategies,
optical optimization and biological applications as well as present comparative discussions on the
www.rsc.org/chemsocrev luminescence mechanisms and characteristics of these three types of luminescent materials.
1. Introduction
Stokes shift is a common definition used in the luminescence
process to describe the energy difference between the maxima
of the excitation and emission spectra peaks. As shown in
Scheme 1, in a typical luminescence process, the luminescence
centre absorbs one excitation photon with energy hn1 or
wavelength l1, and jumps to an excited state 1. After a rapid
non-radiative relaxation process to the excited state 2 with a
loss of a part of the energy, the following emissive transition
from the excited state 2 back to the ground state will generate
photon emission with energy hn2 or wavelength l2. Because of the
restriction of the law of energy conservation, the energy of the
emitted photon must be less than that of the excitation one.1,2
In recent years, anti-Stokes shift luminescent materials have Scheme 1 Schematic illustration of typical Stokes shift (left) and anti-Stokes
attracted much attention because of their unique ability to shift luminescence processes (right).
convert long wavelength (low energy) excitation photons to
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.
View Article Online
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2016
View Article Online
to excite a molecule from one state, e.g. ground state (0), to a luminescence process occurs at higher vibrational levels of the
higher energy level (1) which then jumps back to the ground singlet ground state, it may prefer molecules with rich vibrational
state by generating one photon with higher energy than either energy levels and is strongly temperature dependent due to the
of the absorbed photons. During the TPA process, a non- fact that the populations of higher vibration energy levels (0 0 )
stationary (virtual) state will emerge (illustrated by the dashed are determined by the Boltzmann distribution. Additionally,
line in Scheme 2) due to the interaction of photons and the populations of higher vibrational energy levels are very
Published on 14 December 2016. Downloaded by University of California - San Diego on 14/12/2016 13:06:37.
molecules. However, this virtual state does not exist indeed, limited so that effective anti-Stokes luminescence is usually
and thus the probability of occurrence of TPA is low. This observed in dye molecules with high quantum yield and molar
phenomenon results in an ultra-low cross section of TPA, which extinction coefficient. It is also worth noting that hot band
means that the realization of two-photon excitation lumines- absorption lies in the long wavelength tail of the whole absorption
cence needs extremely high excitation energy to ensure a large band. Dye molecules with small Stokes shifts will exhibit an
number of excitation photons. The experimental proof of optical absorption feature that more portions of the absorption
TPA was demonstrated in 1961, largely attributed to the invention spectrum extend to the long wavelength region of the emission
of lasers. Femto-second pulse lasers are commonly used in the band, and thus will have greater chances of generating hot band
commercial imaging systems for realizing luminescence signals absorption anti-Stokes luminescence.
of two-photon absorption.6 Until the establishment of a two-
photon fluorescence microscope in 1990, the application of this 2.3 Upconversion process
anti-Stokes luminescence process in the biological field just really
In the 1960s, the upconversion process was discovered and then
started. During the development of devices for TPA fluorescence
was quickly established to generate anti-Stokes shift luminescence.
imaging, the investigations of highly efficient TPA dyes were in
In the upconversion process (Scheme 2, right), the luminescence
progress at the same time. These dominated TPA dyes share some
centres can absorb energies from two or more photons sub-
common features in their molecular structure, such as conforma-
sequently (e.g. 0 - 2 - 1), and then generate one emission
tional rigidity and strong p conjugation. These features can
photon with higher energy than the one of each individual
significantly increase the TPA cross-sections. On the other hand,
excitation photon (1 - 0). Because of the existence of a real
the addition of an electron donor (D) and acceptor (A) on the
excited intermediate state (2), each process of photon absorp-
terminals of a p conjugated structure to build a D–p–A system is
tion is like a second-order elementary reaction, which has a
also helpful to boost TPA efficiency. Considering that a one-sided
higher degree of probability than the case of absorption of two
D–p–A structure results in only one direction of polarization
photons simultaneously.9
which reduces the TPA capacity, a centrosymmetry molecular
In fact, the upconversion process is generally divided into
structure like D–p–A–p–D is preferred.6 Although efforts have
two typical mechanisms. One typical upconversion mechanism
been made to optimize the molecular structure to enhance the
exists in the lanthanide (Ln)-based upconversion system using
TPA fluorescence, the exciting power density is still extremely high
lanthanide ions as emissive centres (Scheme 3, left). Lanthanide
which is a tough problem to face. Hence, several alternative anti-
ions with long-lived intermediate energy levels could be relatively
Stokes luminescence mechanisms gradually came into view.
stable in excited states. When the ions in excited states (2)
2.2 Hot band absorption process receive excessive energy from photons or other excited ions
(sensitizers), they will reach higher excited states (1).2,9 At this
The phenomenon of anti-Stokes luminescence induced by hot
moment, anti-Stokes luminescence might occur via radiative
band absorption has long been observed, which can be traced
transitions to make the ions come back to the ground states.
back to 1928.7 In this type of anti-Stokes process, additional
In the lanthanide-based upconversion process, the selection of
energy is provided by the heat originated from the original
sensitizers and emitters is very important. Sensitizers should
Boltzmann distribution of the fluorescent dye molecules
have a large absorption cross section and relatively simple
(Scheme 2, middle). While the excitation light, which irradiates
energy level structures to absorb photon energy as much as
the dye molecules, has a longer wavelength (lower energy) than
possible and avoid energy loss by relaxation. As for emitters,
that of the maximum emission, molecules located at a higher
they usually have multiple energy levels, which may generate
vibration energy level (0 0 ), also termed as ‘hot band’, can absorb
these photons and reach the excited state (1). Finally, the
excited state can decay back to the ground state and generate
the common fluorescence emission (1 - 0) whose wavelength
is shorter than that of the excitation light.8 Despite that
the phenomena of hot-band absorption induced anti-Stokes
luminescence have already been confirmed, studies in this field
are still rare for the time being, mainly because the detailed
rules to design efficient dye molecules with this anti-Stokes
luminescence remain unclear. According to the photophysical
characteristics during the hot band absorption process, some
possible principles can still be summarized. Since this anti-Stokes Scheme 3 Schematic illustration of two types of upconversion processes.
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.
View Article Online
emissions varying from the near infrared region to the ultraviolet In the case of the hot-band absorption process, there is no such
region. Sometimes emitters can function as sensitizers to donate mechanism in the system so that the lifetimes under anti-
the energy of excited states to energy transfer media or to other Stokes and Stokes excitations are nearly the same.11 Besides the
emitters to extend the diversity of the spectral lines. Considering luminescence lifetime, the relationship between the excitation
that sensitizers and emitters are usually metal ions, a host lattice power density and emission intensity also reflects the mechanism.
is needed to carry these ions. Crystalline materials with low In the upconversion process, the curve of the emission intensity as
Published on 14 December 2016. Downloaded by University of California - San Diego on 14/12/2016 13:06:37.
phonon energies are good candidate as host lattices because a function of the pump power density is usually nonlinear,
they can reduce phonon assisted nonradiative energy loss and indicating occurrence of a multiple-photon process. In contrast,
enhance radiative emission. Besides, the crystal symmetry of a linear curve will be obtained during the hot-band absorption
the host lattice will affect the energy transfer efficiency and the process, demonstrating the presence of a single-photon process.
splitting of emission spectra.
Another upconversion process is called triplet–triplet
annihilation (TTA)-based upconversion, which employs the 3. Composition and spectral properties
triplet state of dye molecules as an intermediate excited state of anti-Stokes luminescent materials
(Scheme 3, right). This system usually contains two types of
molecular dyes with matched triplet states. The sensitizer Full understanding of the mechanisms of anti-Stokes lumines-
molecules absorb energy from the excitation light and transfer cence processes paves the way for further investigations in this
the energy to the emitter molecules, resulting in a long-lived field. However, in practical works, it is also important to choose
excited triplet state (3T*). When two emitter molecules at anti-Stokes luminescent materials with desirable components
the excited states encounter in the system, the triplet–triplet and optical performances. This section will introduce the composi-
annihilation process with highly efficient fluorescence occurs, tion and spectral properties of these materials and discuss their
driving one emitter molecule to an excited singlet state (1S*) similarities and diversities. As to similarities in composition, all
through consuming two triplet excited states.2 Similar to the three types of anti-Stokes shift luminescent materials have emissive
Ln-based upconversion system, sensitizers for the TTA-based components with abundant and stable intermediate energy levels.
upconversion process should also have a large absorption cross- As to lanthanide and TTA-based upconversion materials, they share
section at the excitation wavelength. In addition, sensitizers more commonalities. For example, sensitizers and emitters are
should exhibit high intersystem crossing efficiency to generate necessary in both kinds of materials to accomplish the upconver-
a plenty of triplet states and their phosphorescence decay rate sion process effectively. Nonetheless, there still exist quite a lot
should be slow enough to allow triplet–triplet energy transfer differences among these materials due to the extensive sources of
(TTET) to emitters. To realize TTET, the emitter used in the TTA ingredients, from inorganic to organic.
process should have a triplet state with energy comparable to The optical performances of luminescent materials play a
that of the sensitizer and the lifetime of its triplet state should be decisive role in discovering new phenomena and extending the
long enough to ensure the occurrence of the energy transfer. scope of applications. Comparisons of some optical properties
Moreover, the fluorescence quantum yield of the emitter should of these materials are summarized in Table 1 in accordance
be high to obtain efficient upconversion emission.2 with the reported studies, from which we can see that these
materials have remarkable differences in some performances,
2.4 Differences among anti-Stokes shift luminescence such as the full width at half-maximum (FWHM) of the emission
processes peak, anti-Stokes shift, luminescence lifetime, etc. Researchers,
These three types of anti-Stokes shift luminescence processes especially novices, can choose desirable materials for their own
based on different luminescence mechanisms can efficiently works by referring to this table.
generate short-wavelength emission under long-wavelength
excitation, and therefore are all potentially useful in biological 3.1 Two-photon absorption materials
applications. However, for the beginners in this field, it may be TPA dye molecules comprise an electron donor and acceptor
a little bit challenging to distinguish these anti-Stokes shift and a p-conjugated bridge, and usually exhibit relatively high
luminescence processes just by the phenomena of wavelength molecular symmetry. According to the different features in
conversion in experiments. Thanks to the distinctive features of molecular configuration, TPA dyes can be generally divided
their luminescence mechanisms, we can differentiate these into two types with linear and planar geometries, respectively.
processes by investigating some photophysical properties. As to linear molecules, dialkyl and diaryl amino groups are
Firstly, the luminescence lifetimes of upconversion and hot-band widely used as electron donors and many p-deficient hetero-
absorption processes are quite different. In both lanthanide and cycles are designed to be acceptors. The p-Conjugated bridge
TTA-based upconversion systems, sensitizers and emitters are often takes vinylene or ethynylene. The molecular structures of
required simultaneously to accomplish the emission processes D–p–A–p–D with electron-deficient cores have more effective
(Scheme 3). Their luminescence lifetimes are consequently deter- TPA capacity than other types of structures. For planar mole-
mined by the rate of energy transfer (which is slow) rather than cules, porphyrins and expanded porphyrinoids can be adopted
that of emission (which is fast). As a result, much longer lifetimes as chromophores because of their large TPA cross-sections.
can be observed in the upconversion luminescence process.10 In addition, branched planar systems are also qualified to serve
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2016
View Article Online
Excitation power density for bioimaging o55 mW cm2 450 mW cm2 o20 mW cm2 2, 3 and 11–15
Quantum yield o2% o10% o30% 2, 3 and 11
Anti-Stokes shift o80 nm c100 nm 100–300 nm 2, 3 and 11–15
Luminescence lifetime Bns Bms Bms 2, 3 and 11
Photostability Good Excellent Medium 2, 3 and 10–15
Bioimaging level Cell, animal Cell, animal Cell, animal 2, 3, 11, 15 and 29
Coverage of bio-applications Biodetection Biodetection Bioimaging 2, 3, 11, 15 and 29
Bioimaging Bioimaging Tumor targeting
Tumor targeting
Cancer therapy
Metabolism rate Fast Slow Fair 2, 3, 11, 15, 16 and 39
3.2 Hot-band absorption materials Fig. 1 Chemical structures of the reported hot band absorption materials.
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.
View Article Online
extended to about 800 nm. In the normal fluorescence process, rhodamine derivatives. More investigations on other types of
the optimized excitation wavelength is 670 nm or 700 nm. dyes are needed to supplement the alternatives for such anti-
Excitation at 808 nm occurs into the low-energy tail, namely Stokes emission. Theoretically, dyes with high Stokes lumines-
hot band, of the absorption spectrum. Finally, NRh-1 can generate cence quantum yields and broad long-wavelength absorption
anti-Stokes emission centred at 730 nm under 808 nm excitation. edges may be good candidates for hot-band absorption induced
The anti-Stokes emission profile has the same shape and location anti-Stokes luminescence.13 Hence, there is plenty of room for
Published on 14 December 2016. Downloaded by University of California - San Diego on 14/12/2016 13:06:37.
as the conventional Stokes emission spectrum. The normal Stokes improvement and advancement in this realm.
shift of NRh-1 is about 30 nm, while the anti-Stokes shift is
significantly expanded to about 80 nm.
The research of hot band absorption materials is still in the 3.3 Lanthanide-based upconversion materials
primary stage, so the spectral properties of this class of materials Lanthanide-based upconversion nanophosphors (Ln-UCNPs)
have to be summarized from only a few reported works. Detailed are generally composed of a sensitizer, emitter, and host lattice.
optical parameters and spectral profiles are shown in Table 1 Both sensitizer and emitter are lanthanide ions with similar
and Fig. 2, respectively. It can be found that the excitation and chemical properties, which makes the integration of these two
emission ranges of current hot band absorption materials components easy. The commonly used sensitizers are Yb3+ or
mainly cover the long-wavelength part of the visible region Nd3+, because of their relatively large absorption cross section
(Fig. 2). With modification of the molecular structure, the in the near infrared region. The emission colours of lanthanide-
emission wavelength can be expanded to the NIR region (e.g. based upconversion nanomaterials can be modulated by doping
NRh-1, ca. 730 nm).15 According to the results of some recently different types of emitter ions. To circumvent luminescence
published works,11,15 the excitation conditions of hot-band quenching resulted from cross-relaxation between emitter ions,
absorption materials for bioimaging are quite mild, which the doping amount of emitters is controlled at a rather low level
can reduce the excitation source induced thermal effect or (usually o2%). The emitter ions in lanthanide upconversion
photo-damage. The anti-Stokes shifts of hot band materials nanomaterials can be Er3+, Tm3+, and Ho3+. Recently, other
are not very large, but the present filters or other light splitting lanthanide ions, such as Tb3+, Eu3+, Sm3+ and Dy3+, are also
technologies are competent to exclude the interference of developed to serve as emitters through the energy migration
excitation in this case during bioimaging. The most intriguing process or cooperative upconversion mechanism.2,17 The selec-
thing is that hot-band absorption materials are a class of anti- tion of appropriate host materials is also an essential prerequisite
Stokes luminescent materials consisting of simple small mole- for desired optical properties. Lanthanide fluoride nanocrystals
cules. As is well known that small molecules have a much are the preferred upconversion host materials because of their
shorter clearance time than nanomaterials,16 which may reduce ultra-low phonon energy, which results in relatively high quantum
the possible adverse effect to the living body. Hot-band absorp- yield.18 Great efforts have been made in recent years to solve the
tion materials are very promising to serve as optical probes for problem of breaking down the size of lanthanide-based materials
diagnosis and detection in vivo. in the nanoscale for bio-applications. Thanks to the low solubility
One important problem to be addressed is the relatively low of lanthanide fluorides, nearly all wet chemical synthetic methods
luminescence efficiency of hot-band absorption materials. The can be successfully adopted in the synthesis of lanthanide
dyes involved in the reported works are mainly restricted to fluorides, such as co-precipitation, hydro(solvo)thermal synthesis,
thermal decomposition, and sol–gel route synthesis (Fig. 3).
To meet the needs of multifunctional applications and
improve optical performances, the establishment Ln-UCNPs
nanocomposites is quite essential. According to reported
works, the components combined with Ln-based upconversion
materials can be generally classified into metal ions, small
molecules, polymers, amorphous and crystalline inorganic
materials. The construction methods of these composites are
Fig. 2 Typical emission spectra of three types of anti-Stokes luminescent Fig. 3 General illustration of the synthesis of lanthanide-based upconversion
materials. nanoparticles.
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2016
View Article Online
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.
View Article Online
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2016
View Article Online
4. Bio-applications of anti-Stokes
luminescent materials
Published on 14 December 2016. Downloaded by University of California - San Diego on 14/12/2016 13:06:37.
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.
View Article Online
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2016
View Article Online
Weissleder and coworkers utilized Y2O3:Yb,Er upconversion emissive TTA upconversion system into a nanocapsule by the
nanoparticles as a probe for blood vessel imaging.38 Common micro-emulsion method using injectable bean oil as solvent.10
dyes have a shorter life-time in blood than lanthanide-doped The as-prepared nanocapsule has a high quantum yield up to
nanoparticles, causing the difficulty in performing vascular 4.8%. This kind of material which has a relatively fast meta-
imaging using dyes as a probe. Another important usage is bolism rate of about 24 h and rather low toxicity has also been
that these nanoparticles could be used to track the position of used for cell imaging and animal imaging.39 Because of the
labelled cells.3 Although commercial dyes have higher fluores-
Published on 14 December 2016. Downloaded by University of California - San Diego on 14/12/2016 13:06:37.
larger penetration depth of the green light than the blue light,
cence efficiency, they suffer from low stability in cell tracking lymph node imaging can be performed without the removal of
applications. The inorganic lattice makes the signals from skin tissue.
lanthanide-based upconversion nanoprobes ultra-stable, which Because of the higher upconversion luminescence efficiency,
is suitable for long-term observation. Liu and coworkers TTA-upconversion nanoprobes seem to have much more
reported that they can keep tracking cancer cells until they potential in biological applications than lanthanide-based
grow into a solid tumor. This work proved that upconversion upconversion nanoparticles. However, the self-assembled nano-
nanoprobes may not obviously influence the activity of cells.3 particles are susceptible to the surroundings, and the stability of
Anti-Stokes luminescence imaging has superior sensitivity, the developed TTA-based upconversion nanoparticles is yet to be
which is very useful for guiding lesion section during surgery. overcome. Thus, efforts to further enhance the stability of these
However, the penetration depth of the excitation and emission materials are much needed for practical applications.
light still does not meet the requirements of the application in In summary, all of these three types of probes with
clinical diagnosis. Other imaging modes, like magnetic reso- anti-Stokes luminescence can be used in bioimaging. Their
nance (MR) and X-ray computed tomography (CT), have a large common advantages lie in the resistance of background auto-
penetration depth in biotissues, which can compensate for this fluorescence because no anti-Stokes shift luminescence is
shortcoming. Integrating different imaging modes into one generated by biological tissues under identical excitation condi-
contrast agent will greatly improve the accuracy of lesion tions. The near infrared excitation light has a large penetration
localization and reduce the injuries and adverse effects to depth, which makes these probes suitable for in vivo imaging.
patients made by repeated administration of different contrast For the hot-band absorption induced anti-Stokes lumines-
agents. Owing to the abundant physical properties of lanthanide cence of small molecules, their bioimaging applications are
ions, lanthanide-based upconversion nanoparticles have been just in the initial stage. Because such anti-Stokes luminescence
developed for multi-modality imaging. For instance, a nano- emission is a common property of dye molecules under suita-
system serves as an MR contrast agent by introducing ble excitation conditions, there is a plenty of room to further
Gd3+-containing species into the system. For CT imaging, elements improve their performance and broaden the applications of
with larger atomic numbers are favourable. Therefore, Yb3+ and such probes.
Lu3+ are ideal ions to endow the nanoprobes with CT contrast For TTA-based upconversion nanomaterials, a general
ability.2,3 Recently, some radioactive imaging techniques such approach for the preparation of a stable nanosystem containing
as positron emission computed tomography (PET-CT) and both sensitizer and emitter with the ability of free movement is
single-photon emission computed tomography (SPECT) can highly needed at this point of time. If this method is estab-
also use lanthanide-based upconversion nanoprobes for quan- lished, the high upconversion efficiency of the TTA-based
titative imaging.2,3 Li and coworkers used 18F to modify the nanosystem will allow these materials to be used in many
as-prepared lanthanide-based upconversion nanoprobes.2,3 applications.
Similarly, upconversion nanoparticles modified with 153Sm3+ Benefiting from the in-depth investigation of lanthanide-
can serve as contrast agents in SPECT imaging.2,3 The radio- based upconversion nanomaterials in bio-applications, anti-
active imaging techniques can provide real time and quantita- Stokes luminescent probes seem ready to serve as an alternative
tive images of samples with very high spatial resolution. These of the commercial dyes for practical biomedicine where a high
technique could offer new possibilities for the research of signal-to-noise ratio is required. The main concern for the
upconversion nanoprobes and clinical translation. further development is the possible long-term toxicity of these
TTA-based nanomaterials also have been fabricated and probes.3 In addition, because of the low solubility of these
used for small animal bioimaging in recent years. Compared inorganic nanoparticles under biological conditions, they are
with lanthanide-based nanoparticles, these nanomaterials hard to be quickly excreted from living systems, which may
exhibit strong upconversion emission with higher luminescence cause some unwanted side effects and limit their applications.
efficiency, which can be excited with lower power-density lasers.
As mentioned previously, Li and coworkers developed TTA 4.2 Anti-Stokes luminescence materials for biodetection
upconversion nanoparticles with blue emission under green Hot-band absorption dyes whose molecular structures are
excitation by silica coating.24 Although the blue emission is not usually used to design chemodosimeters, can be easily modified
the optimal choice for in vivo applications, cell imaging and to suit the need for biodetection. For instance, the designed NRh
lymph node imaging can be realized under a lower excitation chemodosimeter combines a near-infrared (NIR) frequency
power-density than that in the case using lanthanide upconver- upconversion luminescent rhodamine derivative with a hydrazine
sion nanocrystals as probes (Fig. 10). Later, we integrated a green cyclization reaction site which provides a selective and sensitive
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.
View Article Online
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2016
View Article Online
process, which gives a good description of the energy transfer therapeutic accuracy and mild treatment conditions at the
characteristics in the molecule-to-molecule system, the effective same time.43
energy transfer distance is often believed to be not longer than
10 nm. Nevertheless, this distance will be certainly enlarged for 4.4 Anti-Stokes luminescent materials for secondary
lanthanide-based nanomaterials, because of the relatively longer excitation
lifetime luminescence from lanthanide ions than small molecules.
Anti-Stokes luminescent materials have a unique ability to
Published on 14 December 2016. Downloaded by University of California - San Diego on 14/12/2016 13:06:37.
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.
View Article Online
irradiation at 980 nm has a better killing effect on deep tumor material are in different stages, they all have great potential
in vivo due to its considerable tissue penetration depth (41.2 cm).47 in bio-applications if the corresponding drawbacks of each type
Such upconversion luminescence-driven devices also have of material can be overcome or neglected in specific cases. The
found a place in the bioengineering technology. Han et al. future research will focus on exploring specific applications
embedded dye-sensitized core/active shell upconversion nano- which can maximize the superiorities of anti-Stokes shift
particles in a polymer film to form an implantable device for luminescence, making the materials more valuable for practical
photogenetics.21 Upconversion luminescence generated by
Published on 14 December 2016. Downloaded by University of California - San Diego on 14/12/2016 13:06:37.
applications.
800 nm excitation can effectively activate the channel of
rhodopsin modified neuron cells to show a NIR light intensity
dependent depolarization. Their work offered a very ingenious Acknowledgements
strategy to break the predicament of poor tissue penetration in
The authors thank MOST of China (2015CB931801, 2013CB733703,
present optogenetic tools.
and 2012CB932403), National Natural Science Foundation of China
(21231004, 21375024, and 21527801), and Shanghai Sci. Tech.
Comm. (15QA1400700) for financial support.
5. Conclusions and prospect
In summary, the anti-Stokes luminescent materials indeed Notes and references
have potential in various bio-applications, but the develop-
ments are not balanced at the current stage. 1 J. R. Lakowicz, Principles of fluorescence spectroscopy,
As for the hot-band absorption based anti-Stokes lumines- Springer Science & Business Media, New York, 3rd edn,
cence, it is a general phenomenon for the dye molecules. This 2013.
phenomenon is hard to use in a general wavelength conversion 2 J. Zhou, Q. Liu, W. Feng, Y. Sun and F. Li, Chem. Rev., 2015,
process because of its low efficiency. However, the unique 115, 395–465, and references therein.
anti-Stokes shift luminescence may provide a new excitation 3 J. Zhou, Z. Liu and F. Li, Chem. Soc. Rev., 2012, 41,
method for bioimaging. The temperature-dependent lumines- 1323–1349, and references therein.
cence will also be useful for temperature sensing, especially at 4 G. Chen, H. Qiu, P. N. Prasad and X. Chen, Chem. Rev., 2014,
the microscopic scale. Further research studies are needed for 114, 5161–5214.
the investigation of the relationship between the structure and 5 J. C. G. Bünzli, Chem. Rev., 2010, 110, 2729–2755.
the anti-Stokes luminescence efficiency to provide more probes 6 M. Pawlicki, H. A. Collins, R. G. Denning and H. L. Anderson,
with a wide range of working wavelengths. Angew. Chem., Int. Ed., 2009, 48, 3244–3266, and references
For the TTA-based upconversion nanomaterials, the current therein.
research studies still focus on the development of synthetic 7 R. W. Wood, Philos. Mag., 2009, 6, 310–312.
procedures. Because the sensitizer and emitter molecules need 8 J. L. Clark, P. F. Miller and G. Rumbles, J. Phys. Chem. A,
to be encapsulated in nanoparticles with enough concen- 1998, 102, 4428–4437.
tration, the current developed nanoparticles have a relatively 9 F. Auzel, Chem. Rev., 2004, 104, 139–173.
larger size than the commonly used probes, which may restrict 10 Q. Liu, B. Yin, T. Yang, Y. Yang, Z. Shen, P. Yao and F. Li,
their applications in the living body. The stability of the J. Am. Chem. Soc., 2013, 135, 5029–5037.
assembled nanoparticles is also a concern, which may affect the 11 Y. Liu, Q. Su, M. Chen, Y. Dong, Y. Shi, W. Feng, Z. Y. Wu
upconversion emission. However, this assembled upconversion and F. Li, Adv. Mater., 2016, 28, 6625–6630.
nanoparticles have superior biodegradability than lanthanide- 12 A. V. Kachynski, A. N. Kuzmin, H. E. Pudavar and
based inorganic upconversion nanoparticles, which can be P. N. Prasad, Appl. Phys. Lett., 2005, 87, 023901.
decomposed after the imaging process. If the synthetic route 13 Y. P. Meshalkin, V. A. Svetlichnyi and I. N. Lapin, Russ. Phys. J.,
is well established, the bio-applications of TTA upconversion 2007, 50, 267–274.
nanomaterials can be expected to have a rapid development, 14 S. Kumazaki, Chem. Phys., 2013, 419, 107–112.
because of the high upconversion efficiency and the abundant 15 Y. Liu, Q. Su, X. Zou, M. Chen, W. Feng, Y. Shi and F. Li,
choices of the excitation and emission wavelengths. Chem. Commun., 2016, 52, 7466–7469.
Because of the well-established synthetic routes and lumines- 16 M. Longmire, P. L. Choyke and H. Kobayashi, Nanomedicine,
cence mechanisms, lanthanide-based upconversion nanomaterials 2008, 3, 703–717.
have already been used broadly in many bio-applications as 17 M. Xue, X. Zhu, X. Qiu, Y. Gu, W. Feng and F. Li, ACS Appl.
luminescent probes, especially for research purposes. However, Mater. Interfaces, 2016, 8, 17894–17901.
the relatively low upconversion efficiency and the unclear toxicity 18 S. L. Gai, C. X. Li, P. P. Yang and J. Lin, Chem. Rev., 2014,
originated from the stable crystal lattice of inorganic nanoparticles 114, 2343–2389.
limit their further applications. 19 Y. Lu, J. Zhao, R. Zhang, Y. Liu, D. Liu, E. M. Goldys,
For comparison, three typical types of anti-Stokes lumines- X. Yang, P. Xi, A. Sunna, J. Lu, Y. Shi, R. C. Leif, Y. Huo,
cent materials discussed in this tutorial review have their own J. Shen, J. A. Piper, J. P. Robinson and D. Jin, Nat. Photonics,
superiorities. Although the developments in each type of 2014, 8, 32–36.
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2016
View Article Online
20 W. Q. Zou, C. Visser, J. A. Maduro, M. S. Pshenichnikov and 34 Y.-F. Wang, G.-Y. Liu, L.-D. Sun, J.-W. Xiao, J.-C. Zhou and
J. C. Hummelen, Nat. Photonics, 2012, 6, 560–564. C.-H. Yan, ACS Nano, 2013, 7, 7200–7206.
21 X. Wu, Y. Zhang, K. Takle, O. Bilsel, Z. Li, H. Lee, Z. Zhang, 35 X. Xie, N. Gao, R. Deng, Q. Sun, Q. H. Xu and X. Liu, J. Am.
D. Li, W. Fan, C. Duan, E. M. Chan, C. Lois, Y. Xiang and Chem. Soc., 2013, 135, 12608–12611.
G. Han, ACS Nano, 2016, 10, 1060–1066. 36 H. Wen, H. Zhu, X. Chen, T. F. Hung, B. Wang, G. Zhu,
22 G. Chen, J. Damasco, H. Qiu, W. Shao, T. Y. Ohulchanskyy, S. F. Yu and F. Wang, Angew. Chem., Int. Ed., 2013, 52,
Published on 14 December 2016. Downloaded by University of California - San Diego on 14/12/2016 13:06:37.
This journal is © The Royal Society of Chemistry 2016 Chem. Soc. Rev.