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СHEMISTRY AND TECHNOLOGY OF MEDICINAL COMPOUNDS AND

BIOLOGICALLY ACTIVE SUBSTANCES YTTERBIUM AND ITS PORPHYRIN
COMPLEXES

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 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1

СHEMISTRY AND TECHNOLOGY OF MEDICINAL COMPOUNDS AND BIOLOGICALLY ACTIVE SUBSTANCES

UDK 669.868; 547.979.733
YTTERBIUM AND ITS PORPHYRIN COMPLEXES
V.D. Rumyantseva, senior research scientist, A.S. Gorshkova, student,
A.F. Mironov, head of department
N.A. Preobrazhenskiy Department of Chemistry and Technology of Biologically Active Compounds,
M.V. Lomonosov Moscow State University of Fine Chemical Technologies,
Moscow, 119571 Russia
е-mail: vdrum@mail.ru
he review is devoted to one of the elements in lanthanides group – ytterbium, some of its physicochemical

T properties, use of various ytterbium compounds in chemical reactions, medicine and engineering. The
main attention is paid to ytterbium porphyrins complexes application as sensitive IR-fluorescent probes for
malignant tumors diagnostics.
Keywords: ytterbium, porphyrins, metallocomplexes, fluorescence, life-times, diagnostics, malignant tumors.
Ytterbium was discovered in 1878 by J.
Marignac in the form of ytterbium "earth" –
ytterbium oxide. Name origin goes from Swedish
town Ytterby. The element has 27 isotopes with
mass numbers from 152 to 178; there are 7 stable
isotopes, ytterbium-174 is the most widespread in
the nature. Ytterbium, as well as other lanthanides,
usually forms M3+ ion, but also is capable to show
valence 2. It has small atomic volume and atomic
radius that is explained by effect of "lanthanide
compression" opened by the Norwegian
geochemist Goldschmidt [1]. The effect is shown in
consecutive reduction of rare-earth elements (REE)
ions sizes – from lanthanum to lutetium. Radius of
lanthanum trivalent ion is equal to 1.03 Å, Lu3+ –
0.86 Å [2], and Yb3+ – 1.01 Å [3]. REE ionic
radiuses reduction brings significant distinctions in
their chemical properties, in particular, basicity
decrease, salts solubility change, complex
compounds stability, etc. [4–6]. Characteristic
feature of ytterbium and other REE is a high
paramagnetic susceptibility.
Metal lanthanides are white, in powdery state –
from gray to black color. Rare-earth metals possess
high chemical activity and interact almost with all
elements at rather low temperatures with formation
of stable oxides, sulfides and various salts. Thus,
affinity to oxygen decreases with the atomic
number increase. REE are dissolved in sulfuric and
hydrochloric acids at any concentrations, and also
in the concentrated nitric acid. And, on the
contrary, alkalis don't act on them even when
heating. Interaction intensity with halogens
decreases from fluorine to iodine. REE hydroxides
are basic and bad soluble in water and alkalis.
Elements basicity from lanthanum to lutetium goes
down with ionic radius decrease and ionic potential
increase in the same direction.
Porphyrin molecules form stable complexes with
lanthanide ions which possess intensive absorption in
near infrared region (NIR) [7]. At the same time,
insertion of various substitutes in meso- and/or β-
positions of macrocycle allow to cardinally change
physical and chemical properties of lanthanide
porphyrin complexes that plays an important role
when using them in medicine and photochemistry [8].
In malignant tumors diagnostics porphyrins
attract special attention because of ability to
accumulate in various types of cancer cells and
tumors micro vessels. A number of photosensitizers
which effectively generate singlet oxygen, are
developed for today. Among them porphyrin
derivatives – Photofrin II, Photogem; chlorines –
Foscan, Photoditazin, Photolon, Radachlorin;
phthalocyanines – Photosens; δ-aminolevulinic
acid – Alasens, etc. However, luminescence of
these compounds in tissues is accompanied by
generation of undesirable, in this case, singlet
oxygen. To overcome this drawback, allow purely
diagnostic photosensitizers, thus keeping high
affinity to malignant tumors. Ytterbium complexes
of natural and synthetic porphyrins belong to such
compounds [9].
Now the cancer is on the second place on
mortality after cardiovascular diseases. About 470
thousand primary oncological patients are
registered annually in Russia [10, 11]. According to
WHO forecasts the number of oncological patients
will increase by 50% in 2020 despite considerable
progress in development of various approaches to a
cancer therapy. One of the reasons of such situation
is lack of effective methods of early cancer
detection. By us it was shown for the first time that
ytterbium porphyrins complexes can be effective
labels for luminescent diagnostics of tumors in the
NIR [12].
The first works on synthesis of Yb-complexes of
tetraphenylporphyrin (TPP) derivatives appeared in
1974 [13]. One year later inserion of Yb
mesoporphyrine IX complex in apomioglobin was
carried out [14]. Because of bad dissoluble of REE
inorganic salts in organic solvents, they were replaced
with organic compounds chelates further. So,
ytterbium ion incorporation to porphyrin macrocycle
was carried out with ytterbium acetylacetonate in
quite hard conditions, in the inert atmosphere and in
high-boiling solvent (1, 2, 4-trichlorobenzene) within
several hours.
Ytterbium porphyrins complexes are stable in
the air and in the majority of organic solvents and
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1
therefore can be isolated by a chromatography with
use of various adsorbents [15]. In the case of water-
soluble porphyrins the best results were received
when alloying in imidazole [16].
Works have appeared recently regarding a
microwave radiation application in synthesis of
Er2+ and Gd2+ porphyrin complexes in
dimethylacetamide medium in presence of dry
lithium chloride [17]. In our researches we have
applied this method to Yb tetra-meso-(3-
methoxyphenyl) porphyrin complex synthesis [18].
The Yb-complex was received with an yield 58.4%
YbCl3 + 3CH3COCH2COCH3 + 3NH4OH → Yb(acac)3 + 3NH4Cl + 3H2O
Mediums pH has the main significance at REE
complex compounds synthesis [20] since the type
of lanthanide complexes formation depends on it,
and so does the character of complex formation in
water and in water-organic mediums. When
carrying out the reaction in water with REE salts it
is required that pH of reaction mass doesn't exceed
value at which ytterbium hydroxide is formed.
Value of ytterbium hydroxide sedimentation pH
and its control in the course of synthesis are
necessary conditions when receiving ytterbium
complexes. Used oxygen-containing bidentate
donors (for example, acetylacetone) should be the
low-main. In this connection, reaction between
ytterbium salts with such ligands can be carried out
in neutral and very subacidic mediums (pH 5-6).
Tris-acetylacetonates isolate from water solutions
in a form of hydrates Yb(acac)3×nH2O, where n =
1–4. In Yb(acac)3×H2O series with n = 2, 3, 4 the
structure basis is consist of Yb(acac)×(H2O)2
complexes with three chelate (bidentate)
acetylacetonate groups and two water molecules in
complex internal sphere.
Subsequent purification of ytterbium
porphyrins metallocomplexes is carried out by
means of chromatography methods on silica gel,
aluminum oxide, acrylex R-2 depending on
porphyrin structure.
Luminescence in helate REE compounds with
β-diketones and other organic ligands is observed
only under condition that REE resonant level lies
below triplet level of molecule organic part
(intramolecular electronic excitement energy
transfer) [20]. For example, the luminescence of
ytterbium phthalocyanine complex was not found,
as a result the conclusion was drawn that triplet
level of phthalocyanine ring is located below
ytterbium 2F5/2 resonant level (10300 cm-1) that
received experimental confirmation further. On the
contrary, triplet level of tetrabenzoporphyrine
(TBP) metallocomplexes is located in the range
about 12500 cm-1, i.e. above the Yb3+ 2F5/2 level,
and, therefore, similar complexes are convenient
research objects of intramolecular energy migration
in metalloporphyrin system. Fluorescent spectrum
gives important information about coordination
with use of 1,2-dichlorobenzene and DMFA
mixture (in the ratio 1:9) in presence of dry lithium
chloride. Reaction time 15-20 min, temperature in
microwave oven 145 °C at the power 650 w. Thus,
time of process was considerably reduced, energy
consumptions decreased, reaction was carried out
at lower temperature, there was no need for inert
atmosphere.
REE β-diketones possess high stability [2] and
maintain high temperatures (> 200 °C). Ammoniac
method was applied for REE acetylacetonates
synthesis [19]:
number, bond nature and ytterbium complexes
symmetry. Yb3+ ion has only one multiplet term 2F
related to 4f-electrons; 2F5/2 and 2F7/2 components
of the term are far remote owing to spin-orbital
interaction that gives characteristic Yb3+ transitions
in the NIR.
Adler investigated mechanisms of bond
formation between porphyrin macrocycle and
lanthanide metal ions in 1979 [21]. Buchler carried
out synthesis of several lanthanides porphyrin
complexes and established their dimeric structure
in 1986 [22].
Increased interest in studying of lanthanide ions
luminescence in the NIR (900–1500 nm) is caused
by possibility of application this region for contrast
agents creation for obtaining magnetic resonance
images [23]. Distinctive feature of Yb porphyrins
complexes is the characteristic narrow and rather
intensive luminescence band located in the IR-
region at 975–985 nm in so-called “therapeutic
window of tissues transparency” [24, 25].
There is a significant amount of works both
domestic [26–30] and foreign authors [31, 32]
devoted to study of spectral-luminescent
characteristics of ytterbium porphyrins complexes.
Ytterbium porphyrins complexes were chosen
as research objects because of luminescence
observed at π-electronic molecule part excitement,
the luminescence is caused by Yb3+ ion 4f-electrons
transitions of 2F5/2 →2F7/2 level (2F5/2 – excited
state, 2F7/2 – main state). Ytterbium ion
incorporation in porphyrin leads to decrease in
photochemical activity but thus selectivity of
accumulation in malignant tumors remains the
same as for the majority of porphyrins. Decrease of
quantum yield of singlet oxygen generation is
explained by that luminescent level of Yb3+ ion lies
slightly lower than triplet level of organic molecule
part but higher than that of singlet oxygen. As a
result, porphyrin matrix excitement under influence
of external light radiation is transferred not to
oxygen and intercepted by Yb3+ ion, thereby
harshly reducing singlet oxygen generation
sensitized by porphyrin. These transformations are
shown in fig. 1.
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1

The first works on ytterbium porphyrins

complexes studies as fluorescent labels on animals
with malignant tumors, were carried out on
liposomal forms of coproporphyrin III,
protoporphyrin IX, hematoporphyrin IX (HP) as
methyl ether and 2,4-dimethoxyhematoporphyrin
IX in which acetylacetone residue occupies the
third ytterbium valency [33, 34], and also on water-
soluble derivatives on a basis of 5,10,15,20-
tetrakis(4-carboxyphenyl)porphyrin (TCPP) and
tetrasulfophenylporphyrin (TSPP) in which two
imidazole molecules were ligands [35, 36].
Mice of C57 line with hypodermically
implanted sarcoma 180 cells were used in
researches. Ytterbium porphyrins complexes were
found to mainly accumulate in malignant tumors in
quantities about 10-45 times higher than in near Fig. 1. Scheme of electron transitions in Yb-porphyrin
healthy tissues [22]. Fluorescence spectra and sensitizers and singlet oxygen generation:
luminescence kinetics of a number of Yb- 1 – absorption; 2 – fluorescence;
complexes were also studied: TPP, TSPP, 4-brom- 3 – intercombinational conversion;
and 12-bromsubtituted TPP derivatives, 2,4- 4 – phosphorescence; 5 – excitation transfer
dimethoxyhematoporphyrin IX [37]. to oxygen and singlet oxygen generation ¹O2;
The researches connected with ytterbium 6 – excitation transfer to Yb3+ ion;
isotopes application, are of the special interest. 7 – Yb3+ ion luminescence.
Researches on laboratory animals of Yb porphyrins
complexes as diagnostic labels with use of Hereafter over twenty Yb-complexes of natural
radioactive 169Yb [38] were begun at the end of last and synthetic porphyrins were synthesized [40],
century. Comparative study of accumulation in their electronic spectra and luminescence spectra
healthy and malignant experimental animals tissues (tab. 1) and accumulation in experimental animals
of four ytterbium complexes: TSPP, TCPP, 5- tissues [41, 42] were studied.
phenyl-10, 15, 20-tris(4-sulfophenyl)porphyrin and Temporal and spectral characteristics study of
2,4-dimethoxyhematoporphyrin IX, was carried Yb-complexes of some porphyrins presented in fig. 2
out. It appeared that porphyrins best of all and 3, shows that Yb porphyrins complexes possess
accumulated in tumors, have both hydrophobic and characteristic for rare-earth ions narrow and rather
hydrophilic residues: 2,4-dimethoxyhemato- intensive luminescence band [11] which for ytterbium
porphyrin IX and asymmetrical water-soluble is in the IR-region of 975–985 nm where own
trisulfo-TPP, what is well submit literary data [39]. luminescence of biotissues is practically absent.

Table 1. Main absorption bands of ytterbium porphyrins complexes, λmax, nm

№ Compound В-band Q-bands Solvent
1. Yb-protoporphyrin IX DME 410 540, 578 А*
2. Yb-deuteroporphyrin IX DME 401 533, 569 А
3. Yb-2,4-dimethoxyhematoporphyrin IX 403 537, 572 А
4. Yb-2,4-dimethoxyhematoporphyrin IX dipotassium salt 398 533, 569 В
5. Yb-hematoporphyrin IX TME 408 540, 578 А
6. Yb-coproporphyrin III tetraacid 398 532, 568 В
7. Yb-coproporphyrin III TME 402 532, 570 А
8. Yb-tetraphenylporphyrin 420 513, 549 А
9. Yb-tetrasulfophenylporphyrin 415 550, 587 В
10. Yb-tetra-meso-(p-carboxyphenyl)porphyrin 417 510, 549 В
11. Yb-tetra-meso-(m-methoxy-m-sulfophenyl)porphyrin 416 515, 550 В
12. Yb-tetra-meso-(m-methoxy-p-sulfophenyl)porphyrin 417 514, 548 В
13. Yb-octabromtetramesitylporphyrin 413 585 А
14. Yb-octabrompentafluorophenylporphyrin 465 595 А
15. Yb-octabromtetraphenylporphyrin 472 611, 662 А
Yb-tetra-meso-(1-N-(p-fluorophenyl)-3(o-
16. 430 558, 596 А
chlorophenyl)-pyrazol-4-yl)porphyrin
Yb-tetra-meso-(1-N-(p-methylphenyl)-3(p-fluororphenyl)-
17. 431 557, 596 А
pyrazol-4-yl)porphyrin
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1
Yb-tetra-meso-(1-N-phenyl-3(m-methoxyphenyl)-
18.
pyrazol-4-y)porphyrin
19. Yb-tetra-meso-(p-tolyl)porphyrin
20. Yb-tetra-meso-mesitylporphyrin
21. Yb-tetra-meso-(p-ethylphenyl)porphyrin
DME – dimethyl ether, TME – tetramethyl ether; * А – chloroform, В – 1% sodium bicarbonate solution.
Fig. 2. Luminescence spectrum: 1 – Yb-5,10,15,20-
tetra(1-N-(p-fluorophenyl)-3(o-chlorphenyl)-
pyrazol-4-yl)porphyrin comlex (No. 16);
2 – Yb-2,4-dimethoxyhematoporphyrin IX (No. 3).
It is established that average life-time for
synthesized ytterbium complexes is 5–10 μs that is
significantly higher than life-time of neodymium
porphyrins metallocomplexes (0.72–1.34 μs).
Luminescence decrease has not exponential
character that is caused by strong luminescence
extinguishing by fluctuations of OH-groups in
ytterbium ion immediate environment. As shown in
the fig. 3, life-time of hydrophobic Yb-5,10,15,20-
tetra(1-N-(p-fluorophenyl)-3(o-chlorphenyl)-
pyrazol-4-yl)porphyrin complex (No. 16) has the
maximum about 20 μs that is higher than 11 μs for
amphiphile 2,4-dimethoxyhematoporphyrin IX
(No. 3) and 8 μs for hydrophilic tetracarboxy-
phenylporphyrin (No. 10). Metallocomplex life-
time increase may lead to essential decrease in
applied drug dose at possible retention of contrast
coefficient values (ratio of porphyrin content in a
tumor to its content in near healthy tissue).
Ytterbium asymmetrical tetraarylporphyrins
complexes contained three 4-methoxycarbonyl-
phenyl groups and 4-hydroxyohenyl and 4-
hydroxy-3-methoxyphenyl radicals or isomeric 3-
and 4-pyridyl fragments as the fourth substitute
(fig. 4), were synthesized. Corresponding triacids
were prepared on a basis of triethers by alkaline
hydrolysis [43]. Considerable distinction in excited
state life-times of ytterbium complexes of
asymmetrical porphyrins ethers and acids is shown.
430 557, 596 А
419 512, 548 А
420 513, 549 А
419 512, 549 А
Fig. 3. Curves of luminescence attenuation:
1 – Yb-5,10,15,20-tetra(1-N-(p-fluorophenyl)-
3(o-chlorphenyl)pyrazol-4-yl)porphyrin (No. 16);
2 – Yb-5,10,15,20-tetra(p-carboxyphenyl)-
porphyrin (No. 10); 3 – Yb-2,4-dimethoxy-
hematoporphyrin IX (No. 3).
It turned out that ytterbium complexes of
hydrophobic tri- and tetramethyl ethers have quite
high excited states life-times (13–20 μs) which are
close to values declared by us before, of life-times
for Yb tetrapyrazolylporphyrin complexes (tab. 2)
[40]. In literature for symmetric Yb3+-complexes of
hydrophobic porphyrins luminescence life-time in
the NIR is about 20 μs [15].
Life-time decrease for water-soluble
compounds in comparison with corresponding
three- and tetramethyl ethers complexes is probably
caused by intermolecular hydrogen bonds existence
and luminescence extinguishing by water. In the
review [15] authors noted luminescence intensity
decrease in polar solvents in the following row:
benzene > chloroform > tetrahydrofuran > DMFA
> methanol.
Ytterbium 5-(4-hydroxyphenyl)-10,15,20-tris-
(4-carboxyphenyl)porphyrin complex possesses
shortest life-time (3 μs) and, on the contrary, its
trimethyl ether complex has the highest life-time
(16.3 μs) of all asymmetrical compounds
considered in the work [43]. Molecule symmetry
decrease, due to introduction of one pyridyl
fragment, lowers ytterbium complex life-time in
comparison with corresponding tetra-meso-(4-me-
thoxycarbonylphenyl)porphyrin complex (20 μs).
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1

acac

R R
x 2 Im

N N N N
H3COOC Yb3+ COOCH3 HOOC Yb3+ COOH
N N N N

COOCH3 COOH

1. а. R = 4-OH-Ph 2. а. R = 4-OH-Ph
b. R = 4-Py b. R = 4-Py
c. R = 3-Py c. R = 3-Py
d. R = 4-COOCH3-Ph d. R = 4-COOH-Ph

Fig. 4. Ytterbium tetraarylporphyrin complexes with asymmetrical substitutes.

Table 2. Spectral-luminescent characteristics of Yb porphyrin complexes

UV-vis, λmax, nm Luminescence spectrum τ,

Compound
(ε × 10-3, М-1 sm-1) λmax, nm (DMSO) µs

Yb(асас)-5-(4-OH-Ph)- 424.6 (271), 516 (5.5), 554.4

1a 982 16.3
10,15,20-(4-COOCH3-Ph)3 (15.2),593.2 (4.6)
Yb(асас)-5-(4-Py)-10,15,20-(4-
1b 418, 555.4, 590.8 983 13.4
COOCH3-Ph)3
Yb(асас)-5-(3-Py)-10,15,20-(4-
1c 416.8, 551.4, 588 983 14.8
COOCH3-Ph)3
Yb(Im)2-5-(4-OH-Ph)-10,15,20- 417.4 (128), 549.6 (6.1), 585.6
2a 982 3
(4-COOH-Ph)3 (2.5)
Yb(Im)2-5-(4-Py)-10,15,20-(4-
2b 417 (322), 548.4 (11.7), 585 (2.6) 976 6-7
COOH-Ph)3
Yb(Im)2-5-(3-Py)-10,15,20-(4-
2c 416.8, 551.4, 588.8 983 5
COOH-Ph)3
Yb(асас)-5,10,15,20-
1d 421.4, 515.4, 553, 591.6 974 20
(4-COOCH3-Ph)4
Yb(Im)2-5,10,15,20- 417 (405), 510 (2.5),
2d 980 8
(4-COOH-Ph)4 548.7 (15.6)
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1
Researches into the influence of solvent type
on ytterbium complexes luminescence quantum
yield have shown that use of 20% DMSO aqua
solution instead of water solutions increases the
quantum yield of Yb-2,4-dimethoxyhemato-
porphyrin IX from 0.27 to 0.86.
Fig. 5. Scheme of Yb-2,4-dimethoxyhematoporphyrin IX dipotassium salt synthesis.
Absorption spectra of porphyrins and also their
metallocomplexes in which metal contains an
empty or filled d-shells, are caused by dipolar ππ*-
transitions in visible and near UV-region of
spectrum. This transitions are connected with
transitions of electrons mainly localized on a
porphyrin ligand [46].
Two combinations based on interaction
between two excited configurations in porphyrin
singlet state, are possible: symmetric and
antisymmetric. The strong absorption band B
(Soret band) located on boundary between visible
and UV-regions, corresponds to the first
combination; the less intensive Q-band located in
visible region, corresponds to the second one.
Generally, two characteristic bands Q(υ) and Q(ο)
are observed in metalloporphyrins. The intension
ratio of these bands is accounted for vibronic
Carried out researches allowed to establish that
the most perspective compound for diagnostic
purposes is the Yb 2,4-dimethoxyhematoporphyrin
IX complex (4) (fig. 5). The method of this
substance synthesis is described in works [44, 45].
interaction with Soret band and also the nature of
an axial ligand and substitutes in porphyrin cycle.
Free bases absorption spectra are known to
consist of a strong fundamental Soret band at 370-
420 nm (B-band) and four so-called Q-bands in the
range of 500-600 nm. The Soret band becomes
more intensive and undergoes insignificant
bathochromic shift (8–12 nm) at a complexing.
Besides, two bands (fig. 6) are observed in the
range of 550–600 nm.
Results of pharmacokinetic researches of
Yb(acac)-2,4-dimethoxyhematoporphyrin IX
dipotassium salt on mice-tumorcarriers in 6, 24, 48
and 72 h after an injection are presented in fig. 7.
The maximum tumor/muscle contrast equal 6, was
observed in 48 and 72 h after the drug injection that
testifies to primary accumulation of the Yb
porphyrin complex in a tumor [41].
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1

3
Acute toxicity of Yb-2,4-dimethoxyhemato-
porphyrin IX dipotassium salt was investigated.
2,5
Experiments were carried out on 46 Balb/C mice
for a test-doses definition and a search of the most
2
endurable drug dose. Doses of 125, 150, 175, 200,
250 and 400 mg/kg of animal body weight were
Abs

1,5
used. It was shown that dose of 400 mg/kg
conforms to LD100, of 250 mg/kg – to LD66. The
1
most endurable dose was found to be 125 mg/kg of
body weight for Balb/C line mice [11].
0,5
Accordingly, therapeutic doses lie in a range of 10-
25 mg/kg of body weight. The results obtained
0
350 400 450 500 550 600 650 700
witness indicated a relatively low toxicity of this
nm drug.

Fig. 6. Spectrum of Yb(acac)-2,4-

dimethoxyhematoporphyrin IX absorption
(10-5 М aqua solution).

Fig. 7. Histogram of luminescence intensity distribution of Yb-2,4-dimethoxyhematoporphyrin IX

dipotassium salt in several mouse organs.
Yb-2,4-dimethoxyhematoporphyrin IX
dipotassium salt was used for the first time for a
functionalization of composite nanoparticles
consisted of gold-silver nanocages covered with
silicon dioxide mesoporous cover (fig. 8). The
synthesis technology allows to control nanocages
size in the range of 40-60 nm and silicate cover
thickness from 20 to 100 nm. Besides, the existence
of additional luminescence band of Yb3+ ion in the
range of 900–1100 nm is used for control of
conjugates accumulation and biodistribution by IR-
luminescence method [47, 48]. Such nanostructures
possess a number of important properties, including
easily adjusted plasmonic resonance of nanocages
(650–950 nm) and convenience of silicon dioxide
porous cover functionalization. The appearance of
plasmonic resonance on a surface of Ag-Au
nanoparticles leads to Raman section increase of
studied molecules more than 105–106 times that
allows to investigate molecules conformation at
concentration less than 10-6–10-8 M.
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1

Fig. 8. Scheme of synthesis of composite multifunctional nanoparticles on a basis gold-silver nanocages

covered with silicon dioxide and functionalized by ytterbium hematoporphyrin complex (HP-Yb).
Designations on the scheme: EG – ethylene glycol, PVP – polyvinylpirrolidone, IPA – isopropyl alcohol,
TEOS – tetraethylortosilicate, APTES – 3-aminopropyltriethoxysilan, HP-Yb – ytterbium hematoporphyrin,
EDC – 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, DMSO – dimethyl sulfoxide.
Yb3+ 2,4-dimethoxyhematoporphyrin IX
complexes with bovine serum albumin (BSA) and
in composition with nanoparticles on a lexan basis
and also on a basis of gold nanoparticles with
plasmonic resonance were studied. The complex in
water environment exists in a dimer form with the
size ~ 5 nm. Formation kinetic of its complexes
with BSA and the complexes size came to 20–25
nm, were investigated. Increased affinity to cancer
cells of Yb3+-complexes in nanocomposites was
established [49].
The estimation of ytterbium 4f-luminescence
quantum yield change in symmetric tetrasubstituted
porphyrin complexes with similar structure
contained in meso-position isomeric pyridine
radicals, quinoline and their carbocyclic analogs,
was given by means of “structure – luminescence
quantum yield” models [50]. The received values
of luminescence quantum yields appeared to be
higher than for earlier studied ytterbium complexes
[51] that is probable connected with that the
chromophoric aromatic fragments effectively
accumulated excitement energy, are in all four
meso-positions. In the case when porphyrins are
substituted in four meso-positions by isomeric
pyridine, quinoline and quinoxaline radicals,
luminescent characteristics are higher than in
porphyrins with phenyl, naphthyl and acenaphthyl
substitutes. Obviously, the structural factor caused
by subtle differences in meso-substitutes nature, is
the main reason of distinctions in spectral and
luminescent characteristics as well.
More developed researches on influence of
meso-substitutes and extra-ligands on ytterbium
porphyrins complexes luminescent properties were
carried out later, and it was shown that quantum
yield and life-time of ytterbium ion 4f-
luminescence is higher in complexes with
porphyrins contained aromatic and heteroaromatic
meso-substitutes (in comparison with n-alkyl-
substitutes) and also in complexes with
acetylacetone ion as an extra-ligand [52]. A new
number of ligands – TPP derivatives with various
substitutes in β-positions, were received. For these
compounds 4f-luminescence efficiency depended
on nature of asymmetrical substitutes in porphyrin
macrocycle influenced a positive charge of Yb+3
ion, and on nature of covalent bond between
ytterbium–extra-ligand. Thus, the stronger bond
was, the strongly the effect of Yb+3 "stretch" from
porphyrin macrocycle plane and, respectively, 4f-
luminescence intensity reduction were shown [53].
Similar researches were carried out for
ytterbium octaphenyltetraazaporphyrin complexes
[54]. For them the 4f-luminescence quantum yield
first of all depends on extra-ligand nature. As well
as in the case of ytterbium porphyrins complexes
contained aromatic and heteroaromatic substitutes
in meso-position, luminescence intensity was
higher when using acetylacetonate anion as a
ligand. The ligand, unlike chloride and acetate
anions, is bidentate and, therefore, better protects
Yb3+ ion from solvent molecules which extinguish
4f-luminescence. Comparison of luminescence
quantum yields for ytterbium complexes of
octaphenyltetraazaporphyrin and meso-tetra-
substituted porphyrins confirms the theory that
tetraazaporphyrines are intermediates between
porphyrins and phthalocyanines.
Fluorescent dye – boron-dipyrromethene
(BODIPY) connected with ytterbium ion through
ethynyl bridge, was offered as an extra-ligand in
ytterbium porphyrins complexes [55]. Studies of
photo-luminescent properties of these conjugates
have confirmed the effective energy transfer to Yb-
porphyrin from BODIPY which carried out a role
of an antenna for accumulation of low-energy
visible light. This energy is transferred to the Yb-
complex and sensibilizes ytterbium ion emission in
the NIR (emission time is about 40 ms). Besides,
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1
these conjugates show a two-photon absorption and
a subsequent intensive two-photon-induced
emission in the NIR.
NIR emission properties and singlet oxygen
generation of Ln (Yb3+, Er3+, Nd3+) complexes with
other ligands including texaphyrin derivatives have
were also studied [56].
The first lanthanide complexes with
acetylacetone and asymmetrical meso-substituted
porphyrin – 5-(4-nitrophenyl)-10,15,20-triphenyl-
porphyrin were synthesized in 1999 and the
following structure of complexes (fig. 9) was
offered [57]:
Fig. 9. Structure of Ln(асас)-5-(4-nitrophenyl)-
10,15,20-triphenylporphyrin.
Synthesis of conjugates of covalent-bonded Pd
porphyrin complexes with chiral lanthanide
complexes (fig. 10) in which palladium complexes
acted as an antenna effectively exciting Nd and Yb
emission in the NIR, was described [58]. This
effect was showed especially strongly in oxygen
absence and in nucleic acids presence.
Photo physical and optical properties of a
number of bis-porphyrin complexes contained
ytterbium and transitional metal (Zn, Pd, Pt) ions,
were studied later and their synthesis was
described. Yb3+-porphyrin was connected with the
transitional metal porphyrin complex through a
flexible three-carbon chain, as shown in fig. 11
[59].
Fig. 10. Structural formula of Pd–Ln-complexes.
Fig. 11. Structural formula of Yb–M-complexes.
Researches carried out earlier, have shown that
transitional metal ions with long life-time, such as
Cr3+, Ru3+ and Pt3+ included in d-f-hetero-dimetal
complexes, promote the increase in emission time
of lanthanide ions in the NIR [60-62]. The best
result was observed for the Cr–Ln complex (Ln =
Nd, Yb): lanthanide ions life-time increased from
microsecond to millisecond at 10 K owing to
intramolecular energy transfer from Cr3+ → Ln3+.
Synthesis of bis-porphyrins contained
ytterbium ion in one porphyrin fragment and a
platinum(II) ion in another one, allowed to increase
luminescence intensity in the NIR for five times.
Thus, platinum incorporation in bis-porphyrin
molecule increases luminescence life-time twice.
For other complexes (YbZn and YbPd) the increase
in emission intensity was less significantly.
Lanthanide complexes synthesis (Ln = Ho, Er,
Yb, Lu) on a basis of acetylacetonates and
5,10,15,20-tetra(para-(4-fluorobenzoloxy)-meta-
ethyloxy)phenylporphyrin was carried out and the
photo-generated charge behavior of the ligand and
the complex was investigated by means of surface
photo-voltage spectroscopy (SPS) and field
induced surface photo-voltage spectroscopy
(FISPS) [63].
Ytterbium also finds application as catalysts in
devices for pressure measurement, in X-ray
engineering [64]. Ytterbium triflate – Yb(OTf)3 – is
used as a catalyst for a synthesis of quinolines [65].
REE are used in making of organic light-
emitting diodes (OLEDs) and displays on their
basis possessed a number of advantages in
comparison with plasma (PDP) and liquid crystal
(LCD) displays [66, 67]. The NIR organic light-
emitting diodes on a basis of conjugates of
polymers with lanthanide porphyrin complexes
have found an application in a number of areas,
including telecommunications, biomedicine and
sensors making. The operation of the NIR OLEDs
involves four main steps [68]: 1 – the creation of
singlet (and triplet) excitions on the polymer host;
2 – exciton transport and energy transfer to the
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1
Ln-complex; 3 – localization of the exciton on the
Ln-ion to afford its F-centered excited state; 4 –
NIR emission. The NIR emission wavelength is
determined by the Ln-ion.
The first works about isolation of anhydrous
tetraphenylporphyrin complexes with lanthanides
Fig. 12. Synthesis of Ln–TPP-complexes.
Improved synthetic method for Ln(TPP)
complexes with various multidentate ligands (L)
such as hydridotris(1-pyrazolyl)borate and (cyclo-
pentadienyl)-tris(diethylphosphinito)cobaltate, has
been developed later. A replacement of extra-
ligand L = Cl/dimethoxyethane by more bulky
ligands led to interaction minimization between the
metal and quenching agents that thereby enhance
photoluminescence yields in the NIR [71, 72].
Convenient method of synthesis of lanthanide
monoporphyrin complexes with general formula
[Ln(Por)(H2O)]Cl (Ln = Yb3+, Er3+; Por = porphyrin
dianion) by use of protonolysis reaction of
lanthanide(III) amide with free porphyrin bases, was
offered. Photoluminescent properties studies of
these complexes showed that porphyrin anion can
excite IR-radiation of Yb3+ and Er3+ ions, acting as
an antenna absorbing visible light and transferring
excitation energy to the lanthanide ion, which then
relaxed in the NIR [15].
Isolation procedure of Yb meso-tetrakis-(4-
carboxyphenyl)porphyrin complexes with amino-
and carboxyl groups was developed for the purpose
of receiving IR-fluorescent Yb-porpyrinato markers
for proteins [73]. Then the spacer – (2-amino-
ethyl)amide of 4-nitrobenzoic acid – was
interposed into porphyrin. The meso-mono-{4-
carbamoyl-[2-aminoethyl-(4-amino-benzoyl)]-
phenyl}-tris-(4-carboxyphenyl)porphyrin was
received after the reduction of nitrogroup, that
porphyrin gave the corresponding complex when
alloyed with Yb(acac)3. Covalent conjugates of
ytterbium complexes with BSA were received.
Ytterbium tetraphenyltetracyanoporphyrazine
complex (fig. 13) has been studied in vitro and ex
vivo as a potential photosensitizer for fluorescence
diagnostics and photodynamic therapy of cancer
[74].
The new complex showed intense absorption
and fluorescence in the “optical window” of
biological tissues. Absorption maximum ~ 590 nm,
(Yb, Tm, Fr, Ho), applied in near-infrared polymer
electroluminescent devices (PLED), were described
in 2001 [69, 70]. The complexes were generated by
the reaction of dilithiotetraphenylporphyrin
bis(dimethoxyethane) with lanthanide trichloride
tris(tetrahydrofuran) salts (fig. 12).
emission maximum ~ 640 nm. Fluorescence
enhancement (a 50-fold increase in quantum yield)
was observed in blood serum. In cultured human
cancer cells, the ytterbium porphyrazine complex
quickly accumulates around the nuclei, presumably
in lysosomes. However, the selectivity of the
complex for the tumor vs. normal tissue is not high
enough, so search for new compound formulations
with higher tumor selectivity remains a topical task.
Fig. 13. Structural formula of Yb
tetraphenyltetracyanoporphyrazine complex.
In the literature, very few lanthanide
complexes, particularly ytterbium (III) complexes,
have been reported to display appealing anti-cancer
activities without photoactivation. Yet, the
cytotoxic activity of ytterbium porphyrins
complexes in the absence of photo-activation has
not been reported.
Several ytterbium porphyrins complexes were
synthesized for studies of cytotoxicity towards
various cancer cell lines [75]: octaethylporpyrin
(14); TPP (15); tetrakis(p-tolyl)porphyrin (16);
tetrakis(p-chlorphenyl)porphyrin (17). Macrocyclic
porphyrin ligands were used as a coordination
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1
scaffold for the transport of lanthanide ions in
cancer cells. Cellular uptake efficacy analysis
indicates that bioavailability of ytterbium
porphyrins complex significantly higher in
comparison with YbCl3, and the higher solubility of
the complex 14 in comparison with other three
complexes results in better bioavailability and, аs a
consequence, hence higher cytotoxicity. The
complex 14 displayed practically 30 and 200-fold
higher cytotoxicity than the clinically used cisplatin
towards HeLa и MCF-7 cells respectively, that
indicates higher complex 14 selectivity to that
cancer cell lines. The anticancer effect reveals
through cancer cells apoptosis that is associated
with the endoplasmic reticulum stress and
mitochondrial dysfunction. Besides, the
investigation results showed that the complex 14 is
stable to demetallation and do not undergo
reduction in a presence of thiol-containing
biomolecules such as glutathione that are located in
a cellular environment. As for other three
complexes, the complex 15 turned out to be
generally less cytotoxic (IC50 = 2.2 to > 10 μM),
and both 16 and 17 did not exhibit significant
cytotoxicity towards all of the studied cell lines
with dosages up to 10 μM. Their cytotoxicity at
higher concentrations have not been determined
owing to their poor solubility in aqueous solutions.
However, all studied ytterbium complexes
(octaethylporpyrin, TPP, p-tolyl and p-chloro-
phenylderivatives) are hydrophobic compounds and
dissolve very restrictedly in water.
CONCLUSION
The results presented in the review reflect
increased interest in ytterbium. This attention, first
of all, is caused by its unique fluorescence in the
NIR. At present there is a significant amount of
drugs for photodynamic cancer therapy in the
world, but there are no merely diagnostic drugs that
do not generate singlet oxygen. 169Yb isotope with
a half-life of 31.8 days can possibly be used as a
diagnostic label.
Materials on the study of physicochemical and
biological properties allow consider ytterbium
complexes of porphyrins as promising markers of
low toxicity for fluorescent diagnosis of malignant
tumors without its free grounds of porphyrins photo
toxicity.
Ytterbium complex of 2,4-dimethoxyhemato-
porphyrin IX is the most perspective of them, it has
perculiar selective accumulation in a tumor to the
majority of porphyrins, is low toxicity, very weakly
generates 1O2, is characterized by an intensive
luminescence signal at 985 nm in a "window of
tissues transparency", its synthesis is rather simple
and available, an application of highly sensitive
apparatus allows to use drug doses from 0.01 to 0.1
mg/kg of live organism weight in diagnostic
purposes. The increased affinity of Yb porphyrins
complexes formed a part of nanocomposites, to
cancer cells have been shown.
 Vestnik MITHT (Fine Chemical Technologies). 2014. V. 9. № 1

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