JP2000239373A - Dendrimers with cyclic polyamine cores and their complexes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal complex having high stability, exhibit high fluorescence ability by selecting the transition metal species, and impart water solubility to the complex by modifying dendrimer terminals. Provide new dendrimers. SOLUTION: A dendrimer having a cyclic polyamine core in which a dendron having a repeating unit containing an aromatic ring is bonded to a cyclic polyamine residue at its focal point.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dendrimer having a cyclic polyamine core and a complex thereof. More specifically, the present invention relates to a dendrimer that can provide a highly stable transition metal complex and exhibit high fluorescence ability by selecting a metal species. Further, the dendrimer of the present invention
Since water solubility can be imparted to the complex by modification of the dendrimer terminal, it is useful as a raw material of a fluorescent analysis reagent in an aqueous system.

[0002]

2. Description of the Related Art In a trivalent lanthanoid cation (hereinafter abbreviated as Ln ³⁺ ) complex having a dendrimer as a ligand, the dendrimer sensitizes Ln ³⁺ to greatly improve its fluorescence ability. Kawa et al .; Chem. Mate
r. 10, pp. 286-296 (1998). This effect is due to the fact that in a complex of Ln ³⁺ with a polybenzyl ether dendrimer that absorbs ultraviolet light, the spatially widely spread dendrimer first absorbs the energy of ultraviolet light as a “light-collecting antenna,” and then converts this energy to the dendrimer. Focal Point
(point: the starting point of the branched structure of the dendrimer) is understood as the “antenna effect” that is transmitted to the lanthanoid cation located at the point where the lanthanoid cation emits light. However, since the complexes according to this report complex stability is relatively low and is in carboxylate salt coordination sites of hydratable Ln ³⁺ is free, Ln ³⁺ in an organic solvent containing water It has been pointed out that quenching due to hydration of liquor is likely to occur. In addition, giving high water solubility to a dendrimer complex exhibiting such an “antenna effect” has been studied so far, for example, although it is expected to be useful as a reagent for fluorescence immunoassay of an aqueous solution such as a blood sample. I didn't.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dendrimer ligand having the same "antenna effect" as described above and providing a highly stable dendrimer complex, and a transition using the same. It is to provide a metal complex. In particular, provision of such a dendrimer complex having both water solubility and fluorescent ability is an issue of high practical value.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive systematic studies on the complexation of Ln ³⁺ with a coordinating organic compound. It has been found that by adopting the specific structure of the above, it becomes possible to provide a dendrimer complex having high complex stability and having both water solubility and fluorescent ability, and completed the present invention.

That is, the gist of the present invention resides in the following 15 items. 1. A dendrimer having a cyclic polyamine core in which a dendron having a repeating unit containing an aromatic ring is bonded to a cyclic polyamine residue at its focal point. 2. 2. The dendrimer having a cyclic polyamine core according to the above 1, wherein the dendron has a polybenzyl ether structure. 3. 3. The dendrimer having a cyclic polyamine core according to the above item 2, wherein the polybenzyl ether structure has a 3,5-dioxybenzyl group represented by the following general formula (1) as a repeating unit.

[0006]

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[0007] 4. 4. The dendrimer having a cyclic polyamine core according to any one of the above 1 to 3, wherein the dendron has an ester group at a non-focal point terminal. 5. 4. A dendrimer having a cyclic polyamine core according to any one of the above 1 to 3, having a carboxylate group at a non-focal point end of the dendron. 6. 6. A dendrimer having a cyclic polyamine core according to any one of the above 1 to 5, wherein the cyclic polyamine residue contains 3 or 4 nitrogen atoms. 7. 7. The dendrimer having a cyclic polyamine core according to the above 6, wherein the cyclic polyamine residue contains 4 nitrogen atoms. 8. 8. The dendrimer having a cyclic polyamine core according to 7, wherein the cyclic polyamine residue is a 1,4,7,10-tetraazacyclododecane residue. 9. 9. A dendrimer having a cyclic polyamine core according to any one of the above 1 to 8, wherein the dendron is directly bonded to a nitrogen atom of the cyclic polyamine residue. 10. A transition metal complex having a dendrimer having a cyclic polyamine core according to any one of the above 1 to 9 as a ligand. 11. 11. The transition metal complex according to the above 10, wherein the transition metal emits light by excitation light having an absorption band wavelength of a dendron residue. 12. The above 10 or 1, wherein the transition metal is a lanthanoid
2. The transition metal complex according to 1. 13. Lanthanoid is a terbium trivalent cation (T
13. The transition metal complex according to the above 12, which is b ³⁺ ). 14． Lanthanoid is a europium trivalent cation (Eu
13. The transition metal complex according to the above 12, which is ³⁺ ). 15. 15. The transition metal complex according to any one of the above 10 to 14, wherein the counter anion is a trifluoromethanesulfonate anion.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. <Dendron> Dendron (Dendr) in the present invention
The term "on)" is an agreement with a term widely used in the meaning of a molecular building component having such a structural unit in the research of dendrimers (Dendrimer: a generic name of polymer structures having dendritic ordered branches), which has recently become popular. Yes, for example, G. R. Newcome by Newkome et al .; De
ndritic Molecules, Concept
s ・ Synthesis ・ Perspectives
(VCH Verlagsgesellschaftm
bH; Weinheim, Germany; 1996;
ISBN: 3-527-29325-6). The starting point of the branch structure (corresponding to the pivot of the fan when the dendron is schematically considered to be a sector) is called a focal point, and the order of the branch is referred to as “generation (Genera).
)) (see FIG. 1). The number of branches at the branch point of the dendron in the present invention is not limited, but is usually two (in the case of FIG. 1) or three, and preferably two. In the present invention, a structure having one branch point (that is, the first generation) is also regarded as a dendron.

The dendron used in the present invention needs to have an aromatic ring in the repeating unit of its chemical structure. This is because the dendron exhibits the above-mentioned "antenna effect" by absorbing ultraviolet light or visible light. Here, the aromatic ring means, for example, a hydrocarbon aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring, and a nitrogen-containing aromatic ring such as a pyridine ring and a quinoline ring. As a structural example of the dendron suitable for the present invention, specifically, aromatic polyethers such as polybenzyl ether, aromatic polyesters such as polyhydroxybenzoic acid, aromatic or semi-aromatic polyamide, aromatic polycarbonate, aromatic polycarbonate Polyester carbonate, aromatic polysulfide such as polyphenylene sulfide, aromatic polyimide including aromatic polyimide, aromatic polyamide imide and other elements other than carbon in the polymer main chain, aromatic polymer structure, polyphenylene, polyphenylene ethynylene, carbon such as polyphenylene ethylene -Aromatic conjugated polymer structures in which the main chain is composed of carbon bonds, among which aromatic polyethers such as polybenzyl ether, aromatic polyesters such as polyhydroxybenzoic acid and the like are preferable, and Aromatic polyethers such as benzyl ether More preferably ethers represented by the following general formula (1)
A structure having a 3,5-dioxybenzyl group represented by a repeating unit (CJ Hawker et al .; J. Chem.
Soc. Chem. Commun. , 1010-10
Page 13 (1990)). Incidentally, these plural kinds of structures may coexist in one dendron.

[0010]

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There is no particular limitation on the generation of the dendron used in the present invention, but it is usually 1 to 6, preferably 1 to 4 in terms of easiness of synthesis, more preferably 2 to 4 in terms of luminous effect, and most preferably 3 to 3. Or 4. A practically important problem of the present invention is to provide a dendrimer complex having both water solubility and fluorescence, and as a means for solving this problem, there is a modification of a non-focal point end of a dendron. This is primarily due to the fact that dendrimers show spatial expansion of spherical molecular chains, especially in higher generations, due to the crowding of their branched chains, so that the non-focal point end, which is thought to be located near its surface, This is because the chemical properties have a very large effect on the solubility of the dendrimer molecule. Secondly, the above-mentioned document by Kawa et al. States that absorption of light due to the structure at the end of the non-focal point has a large effect on the above-mentioned "antenna effect". This is because it is expected that the chemical structure of this terminal is important for the fluorescence ability of.

[0012] Therefore, it is important to introduce a functional group at the non-focal point terminus of the dendron at the non-focal point terminus, such as an ester group at the non-focal point terminus of the dendron. And dendrimers having the formula: This is because the ester group can be easily converted to a water-soluble carboxylate salt by alkali hydrolysis, and a new structure can be introduced into a terminal by a transesterification reaction or an ester-amide exchange reaction (for example, Leo
n, J. et al. W. J. et al. Am. Chem. Soc. , 11
8, 8847 (1996)).

<Cyclic Polyamine> The term “cyclic polyamine” in the present invention is an n + 1 secondary amino group (n is a natural number of 1 or more) represented by the following general formula (2).
Means a cyclic molecular structure linked by n + 1 divalent hydrocarbon residues R. However, in Formula (2), a plurality of Rs may be different from each other. Specific examples of _{R, -CH 2 -, - (CH} 2) 2 -, - (CH 2)
_{3 -, - (CH 2)} 4 -, - (CH 2) 5 -, - (CH
_{2) 6} - or the like having a carbon number of 6 or less methylene chain, isopropylene group, isobutylene group, a methylene chain having a branch, such as isopentylene, m- phenylene group, etc. phenylene group such as p- phenylene group and the like, cyclic From the viewpoint of the coordination ability of the polyamine residue to the transition metal,-(CH ₂ ) _2- ,
A methylene chain having 2 to 4 carbon atoms represented by-(CH ₂ ) _3- and-(CH ₂ ) _4- is preferable, and-(CH ₂ ) _2-
Or - (CH _{2) 3} - methylene chain represented by is most preferable.

[0014]

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The structures of the cyclic polyamine which can be suitably used in the present invention include 1,4,7-triazacyclononane,
1,4,7,10-tetraazacyclododecane, 1,
4,7,10,13-pentaazacyclopentadecane,
1,4,7,10,13,16 hexa aza cyclooctadiene decane of - (CH _{2) 2} - cyclic polyamines linked by a chain, 1,5,9-triazacyclododecane,
1,5,9,13- tetraazacyclododecane cyclohexadecane etc. - (CH _{2) 3} - cyclic polyamines linked by a chain,
1,4,8,11 tetraazacyclotetradecane etc. - (CH _{2) 2} - chain and - (CH _{2) 3} - cyclic polyamines linked by a chain and the like. Among these, 1,4,7-triazacyclononane, 1,4,7,10-tetraazacyclododecane, 1,5,9-triazacyclododecane, and among these, preferred are those capable of coordinating to transition metals. 1,
Cyclic polyamines having 3 or 4 nitrogen atoms, such as 5,9,13-tetraazacyclohexadecane, and more preferably 1,4,7,10-tetraazacyclododecane or 1,5,9, Cyclic polyamines having 4 nitrogen atoms, such as 13-tetraazacyclohexadecane, are most preferred, and 1,4,7,10-tetraazacyclododecane (commonly known as cyclen) is preferred.

<Dendrimer> The dendrimer in the present invention means a structure in which the above-mentioned dendron is bonded to a cyclic polyamine residue. The number of dendrons constituting the dendrimer of the present invention is not particularly limited, but usually 2 to 6, preferably 2 to 4, more preferably 3 or 4, and most preferably 4 in terms of luminous efficiency. Number. Also, plural kinds of dendrons may be bonded to one cyclic polyamine residue. The dendron used in the present invention needs to be combined with the cyclic polyamine residue at its focal point to form a dendrimer. Here, the cyclic polyamine residue means a structure which is missing because an arbitrary hydrogen atom of the cyclic polyamine is substituted with a dendron. The bonding mode between the dendron and the cyclic polyamine residue is not particularly limited, but specific bonding structures include, for example, an ether bond, an ester bond,
Examples include an amide bond, a carbon-carbon bond, and a carbon-nitrogen bond. Particularly preferred from the viewpoint of light emission characteristics is a case where the compound is directly bonded to a nitrogen atom of a cyclic polyamine residue by a carbon-nitrogen bond.

<Transition Metal Complex> The dendrimer of the present invention is
A transition metal complex as a ligand is contained in the dendrimer.
Atom of cyclic polyamine residue coordinated to transition metal
Having a structure. The transition metal in the present invention is an atomic number
Is 21 to 31, 39 to 50, 57 to 82, or 89
An element corresponding to any of
In the form of Where transition metals are used in the form of cations
In this case, the counter anion is included in the complex. History of the present invention
Preferred transition metal from the viewpoint of utilizing the luminescence of the transfer metal complex
Is that fluorescence in the ultraviolet to infrared wavelength range is usually important
And Cr as a specific cation ³⁺, Mn³⁺, Mn⁴⁺,
Fe²⁺, Fe³⁺4th cycle transition causing 3d electron transition such as
Transfer metal cation, Cu⁺, Ag⁺, Au⁺Genus 1B
Ion, Ga⁺, In⁺, Tl⁺3B cations such as
Sn²⁺, Pb²⁺4B cations such as Ce, etc.³⁺, Pr ³⁺,
Nd³⁺, Nd⁴⁺, Sm²⁺, Sm³⁺, Eu²⁺, Eu³⁺, T
b³⁺, Dy³⁺, Dy ⁴⁺, Ho³⁺, Er³⁺, Tm²⁺, Tm
³⁺, Yb²⁺, Yb³⁺Lanthanoid cations and the like
Can be Among these, Pr³⁺, Nd³⁺, Sm²⁺, S
m³⁺, Eu²⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er
³⁺, Tm³⁺, Yb³⁺Lanthanoid cations are visible
~ Fireflies with features such as near-infrared region, long life, narrow wavelength width
It is particularly important because it emits light.³⁺When
Eu³⁺Is practical in terms of the efficiency of the "antenna effect"
Most important.

The method for producing the transition metal complex of the present invention is particularly limited.
No transition in solution for the dendrimer of the present invention
Method of reacting metal cation salt, cyclic polyamine
Complexation with a transition metal cation salt acting beforehand
Then, there are methods to bind dendron, etc.
It is. Particularly preferably used in these exemplified methods
Transition metal cation salts are counter-anion soluble in organic solvents
Having, for example, trifluoromethanesulfone
To anion (commonly known as triflate anion: CF _ThreeSO_Three
^-), BF_Four ^-, ClO_Four ^-, PF₆ ^-With something like
Yes, especially CF_ThreeSO_Three ^-Is optimal. Therefore,
Using these anions as counter anions of transition metal cations
The containing transition metal complex is most suitably produced.

[0019]

EXAMPLES Specific examples of the present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist of the present invention.
Reagents and resins used were A unless otherwise noted.
The one supplied by ldrich was used.

[Measurement apparatus and conditions, etc.] (1) ¹ H-NMR GSX-270 type FT-NMR (270M) manufactured by JEOL
Hz), solvent: CDCl _3. Room temperature measurement. The standard is CDC
It was the signal of 7.28ppm of l _3. (2) Absorption spectrum: V560 absorption spectrophotometer manufactured by JASCO (using a 1 cm quartz cell). Room temperature measurement. (3) Emission spectrum: FP-777W manufactured by JASCO
Fluorometer (using 1 cm quartz cell). Room temperature measurement. 1. Synthesis of dendron 1-1) Benzyl terminal dendron Hawker, C.I. J. J. et al. Am. Chem. So
c. , 112, 7638 (1990).
Next-generation and third-generation dendritic benzyl bromides (compounds abbreviated as [Gn] -Br in the literature, where n is a natural number representing the generation of dendrons, and hereinafter abbreviated in the same manner) were synthesized.

1-2) Ester-terminated dendron Gerrit, L .; Chem. Commun. , 2
143 (1996), 3,5-bis {3,5-bis (tert-butyldiphenylsilyloxy) benzyloxy} benzyl alcohol (hereinafter referred to as S
abbreviated as iG1-OH; represented by compound 7 in the literature). On the other hand, Hawker, C, J. et al. J. et al. Chem.
Soc. Perkin Trans. 1, 1,287 (1993), 3,5-bis (4-methoxycarbonylbenzyloxy) benzyl bromide (hereinafter abbreviated as EG1-Br; represented as compound 4 in the literature). The thus obtained SiG1-OH (1.0 equivalent) and E
G1-Br (4.4 equivalents), 18-crown-6 (1.
6 equivalents) and potassium fluoride (20 equivalents) were stirred in dry acetone for 24 hours while heating under reflux. After concentration, this was dissolved in methylene chloride, washed with water, dried over magnesium sulfate, filtered, and concentrated. This was purified by silica gel column chromatography (eluted with a methylene chloride-diethyl ether system) to obtain a third-generation dendritic benzyl alcohol having a 4-methoxycarbonylbenzyl group at the terminal (hereinafter, abbreviated as EG3-OH). ).
EG3-OH is dissolved in dry tetrahydrofuran (THF), and carbon tetrabromide (2.5 equivalents) and triphenylphosphine (2.5 equivalents) are sequentially added with stirring, and silica gel thin-layer chromatography containing an ultraviolet sensitizer. (Mer
The two reagents were appropriately added in 0.8 equivalents until the spot of the raw material EG3-OH disappeared in the case of ck Co., Ltd.). After pouring the reaction mixture into a large excess of water, the reaction mixture is extracted with methylene chloride, purified in the same manner as in the preparation of EG3-OH, and subjected to a third-generation dendritic benzyl bromide having a target methyl ester terminal (hereinafter referred to as EG3OH). -Br).
The structure of this compound, ¹ H-NMR spectrum of the supra Hawker, C, J. J. et al. Chem. Soc. P
erkin Trans. 1, page 1287 (1993)
In the same substance (represented as compound 8 in the literature). 2. Synthesis of Dendrimer by Bonding of Dendron to Cyclic Polyamine (See FIGS. 2 to 4 for Structural Formulas) 2-1) 1,4,7,10-Tetraazacyclododecane (hereinafter, a common name of cyclen is used)

Example 1 Cyclen (1 equivalent) [G-
1] -Br (4.2 equivalents) and anhydrous potassium carbonate (20 equivalents) were dried with N, N-dimethylformamide (DMF)
The mixture was stirred at 70 ° C for 40 hours. The reaction solution was poured into a large excess of water while stirring, and the precipitate was separated by filtration. The precipitate separated by filtration was extracted with methylene chloride, concentrated, and purified by column chromatography on alumina using methylene chloride as a developing solvent. The purified product was dissolved in methylene chloride and further purified by reprecipitation in methanol to obtain a compound in which four [G-1] dendrons were bonded to each nitrogen atom of the cyclen (hereinafter, abbreviated as G1Cy). ). The structure was confirmed by ¹ H-NMR that the benzylic position derived from the dendron and the proton of the aromatic ring and the methylene proton derived from the cyclen (2.7 ppm) were clearly observed, and that the integral value ratio supported the expected structure. did.

Example 2 In Example 1, 1- was used in place of [G-1] -Br.
A similar experiment was performed using [G-3] -Br prepared in 1) to obtain a compound in which four target [G-3] dendrons were bonded to each nitrogen atom of the cyclen (hereinafter, referred to as “G-3”). G
3Cy). The structure was confirmed by ¹ H-NMR in which the benzyl position and the aromatic ring proton derived from the dendron and the methylene proton derived from the cyclen (2.7 ppm, broad) were observed, and the integral value ratio supported the expected structure. did.

Example 3 In Example 1, 1- was used in place of [G-1] -Br.
A similar experiment was performed using EG1-Br prepared in section 2).
The target EG1 dendron has four cyclens
A compound bonded to each nitrogen atom was obtained (hereinafter, EG1Cy)
Abbreviated). The structure is ¹In H-NMR, the dendron-derived
Methoxy group, benzyl position, aromatic ring proton,
Methylene protons derived from Clen (2.7 ppm)
And the integral ratio supported the expected structure.
confirmed.

Example 4 In Example 1, 1- was used in place of [G-1] -Br.
A similar experiment was performed using EG3-Br prepared in section 2).
And the target EG3 dendron has four
A compound bonded to each nitrogen atom was obtained (hereinafter, EG3Cy)
Abbreviated). The structure is ¹In H-NMR, the dendron-derived
Methoxy group, benzyl position, aromatic ring proton,
Methylene protons derived from Clen (2.7 ppm, blow
C) are observed, and the integral ratio also supports the expected structure.
It was confirmed from that. 2-2) 1,4,7-triazashi
Chrononan

Example 5 1,4,7-Triazacyclononane (1 equivalent), 1-
[G-3] -Br (3.15 equivalents) prepared in 1),
Anhydrous potassium carbonate (15 equivalents) was stirred in dry N, N-dimethylformamide (DMF) at 70 ° C. for 30 hours. The reaction solution was treated and purified in the same manner as in Example 1 to obtain a compound in which three target [G-3] dendrons were bonded to the respective nitrogen atoms of 1,4,7-triazacyclononane (hereinafter, referred to as “D-3”). G1Tr). The structure was determined by ¹ H-NMR, where the benzyl position derived from dendron and the proton of the aromatic ring, 1,4,
The methylene protons derived from 7-triazacyclononane were clearly observed, and the integrated value ratio was confirmed by supporting the expected structure.

Example 6 In Example 5, 1- was used instead of [G-3] -Br.
A similar experiment was carried out using EG3-Br prepared in section 2), and three EG3 dendrons of interest, 1, 4, 7
-A compound bound to each nitrogen atom of triazacyclononane was obtained (hereinafter abbreviated as EG3Cy). The structure is ¹ H-NM
At R, a methoxy group derived from the dendron, a benzyl-position proton, and an aromatic ring proton, and a methylene proton derived from 1,4,7-triazacyclononane were observed, respectively, and the integral value ratio was confirmed by supporting the expected structure. did. 3. Preparation of complex consisting of dendrimer and Ln ³⁺

Example 7 G1Cy (1.0 equivalent) synthesized in Example 1 was charged into a reaction vessel.
, And vacuum drying and nitrogen substitution were repeated. Meanwhile, tell
Biium (III) trifluoromethylsulfonate T
b (CF_ThreeSO_Three)_Three(5.0 equivalents) to another reaction vessel
And then repeat vacuum drying and nitrogen replacement, then dry DMF
To dissolve and add a small amount of trimethyl orthoforme.
The mixture was added as a dehydrating agent and stirred at 65 ° C. for 1 hour. This
Add the DMF solution to the container containing G1Cy prepared earlier.
Then, the mixture was stirred at 70 ° C. for 4 days. After concentrating the reaction mixture under reduced pressure, salt
Dissolved in methylene chloride and filtered. This filtrate is n-hexane
The re-precipitate generated by throwing in while stirring is filtered off,
It was again dissolved in methylene chloride and filtered. Thus obtained
The filtrate obtained is subjected to the same reprecipitation, filtration of the precipitate, dissolution and filtration.
Purification was performed by repeating each operation, and finally, the resultant was concentrated and dried. like this
The product obtained ¹In H-NMR, compared to G1Cy
To give a significantly broadened signal, and G1
The large shift in the chemical shift of each proton of Cy
From the target Tb of G1Cy³⁺Complex formed
(Hereinafter abbreviated as G1Cy-Tb).

Example 8 A similar experimental operation was performed as in Example 7, except that EG1Cy was used instead of G1Cy. The product thus obtained is
^{In 1} H-NMR, a signal that was significantly broader than that of EG1Cy was given, and the chemical shift of each proton of EG1Cy was largely shifted, so that the target Tb ³⁺ complex of EG1Cy was formed. (Hereinafter abbreviated as EG1Cy-Tb).

Example 9 In Example 7, instead of terbium (III) trifluoromethylsulfonate Tb (CF ₃ SO ₃ ) ₃ , europium (III) trifluoromethylsulfonate E
The same experimental operation was performed using u (CF ₃ SO ₃ ) ₃ . The product thus obtained was analyzed by ¹ H-NMR for G1C
Since a signal that was significantly broader than that of y was given and the chemical shift of each proton of G1Cy was largely shifted, it was considered that the desired Eu3 ⁺ complex of G1Cy was formed (hereinafter, G1Cy−). Eu).

Example 10 In Example 9, terbium (III) trifluoromethylsulfonate Eb was replaced by europium (III) trifluoromethylsulfonate E instead of Tb (CF ₃ SO ₃ ) ₃
The same experimental operation was performed using u (CF ₃ SO ₃ ) ₃ . The product thus obtained was identified by ¹ H-NMR as EG1
Since a signal that was significantly broader than that of Cy was given and the chemical shift of each proton of EG1Cy was largely shifted, it was considered that the desired Eu ³⁺ complex of EG1Cy was formed (hereinafter, EG1Cy−). Eu). 4. Emission evaluation of complex consisting of dendrimer and Ln ^{3+ The} complex obtained in the above example was dissolved in dry acetonitrile, and the main luminous body wavelength (T
The excitation spectrum measured at 545 nm for the b ³⁺ complex) was measured. As a result, emission at 282 nm that was considered to be derived from the dendron was observed. Then 282 nm
When the luminescence of the acetonitrile solution by the excitation light was measured, the Tb ³⁺ complex of Example 7 (G1Cy-Tb) and the Tb ³⁺ complex of Example 8 (EG1Cy-Tb) both showed strong Tb ³⁺ Since an emission band was observed, and a broad emission band near 310 nm derived from the dendron was hardly observed, the energy transfer from the dendron to Tb ³⁺ was performed with extremely high efficiency by the above-mentioned “antenna effect”. It turned out to have happened. 5. Synthesis of water-soluble dendrimer ligand

Example 11 Ester-terminated dendrimer EG3C synthesized in Example 4
y was dissolved in a mixed solvent system of methanol / THF / water, and the ester group was hydrolyzed by treating with a double equivalent of potassium hydroxide with respect to the ester group. This solution was purified by dialysis to remove excess potassium hydroxide, and concentrated to obtain a third-generation dendrimer in which the target ester terminal was hydrolyzed to a carboxylate group (abbreviated as CG3Cy).
This structure was confirmed by ¹ H-NMR (deuterated water) from the complete disappearance of the signal of the methoxy group derived from the raw material dendrimer.

[0033]

The dendrimer having a cyclic polyamine core of the present invention provides a transition metal complex having high stability, and the complex exhibits high fluorescence ability by selecting a metal species, for example, by using a lanthanoid cation. Also, since the complex can be made water-soluble by modifying the dendrimer terminal, for example,
It is useful as a raw material for a fluorescent analysis reagent in an aqueous system.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing dendrimer generations and focal points.

FIG. 2 is a schematic diagram showing the structure of a cyclen-based first generation dendrimer.

FIG. 3 is a schematic diagram showing the structure of a cyclen-based third generation dendrimer.

FIG. 4 is a schematic diagram showing the structure of a 1,4,7-triazacyclononane-based third generation dendrimer.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Manabu Kawa 1000-F, Kamoshida-cho, Aoba-ku, Yokohama-shi, Yokohama-shi F-term in Yokohama Research Laboratory, Mitsubishi Chemical Corporation 4H048 AA01 AB20 AB92 VA20 VA70 VB10 4J005 AA25 BB04 BD05

Claims (15)

[Claims] 1. A dendrimer having a cyclic polyamine core in which a dendron having a repeating unit containing an aromatic ring is bonded to a cyclic polyamine residue at its focal point. 2. The dendrimer having a cyclic polyamine core according to claim 1, wherein the dendron has a polybenzyl ether structure. 3. The dendrimer having a cyclic polyamine core according to claim 2, wherein the polybenzyl ether structure has a repeating unit of a 3,5-dioxybenzyl group represented by the following general formula (1). Embedded image 4. The dendrimer having a cyclic polyamine core according to claim 1, which has an ester group at a non-focal point terminal of the dendron. 5. The dendrimer having a cyclic polyamine core according to claim 1, which has a carboxylate group at a non-focal point end of the dendron. 6. The dendrimer having a cyclic polyamine core according to claim 1, wherein the cyclic polyamine residue contains three or four nitrogen atoms. 7. The dendrimer having a cyclic polyamine core according to claim 6, wherein the cyclic polyamine residue contains four nitrogen atoms. 8. The method according to claim 1, wherein the cyclic polyamine residue has 1,4,7,10
The dendrimer having a cyclic polyamine core according to claim 7, which is a tetraazacyclododecane residue. 9. The dendrimer having a cyclic polyamine core according to claim 1, wherein the dendron is directly bonded to a nitrogen atom of the cyclic polyamine residue. 10. A transition metal complex having a dendrimer having a cyclic polyamine core according to claim 1 as a ligand. 11. The transition metal complex according to claim 10, wherein the transition metal emits light by excitation light having an absorption band wavelength of a dendron residue. 12. The transition metal complex according to claim 10, wherein the transition metal is a lanthanoid. 13. The transition metal complex according to claim 12, wherein the lanthanoid is a terbium trivalent cation (Tb ³⁺ ). 14. The transition metal complex according to claim 12, wherein the lanthanoid is a europium trivalent cation (Eu ³⁺ ). 15. The transition metal complex according to claim 10, wherein the counter anion is a trifluoromethanesulfonate anion.