Fluorescent polymer fine particle, method for forming thereof, fluorescence detection kit, and method for detecting fluorescence

A fluorescent polymer fine particle comprising:

• a polymer particle having a core-shell configuration comprising a hydrophobic core and a hydrophilic shell;
• and
• a fluorescent lanthanoid dye that is integrated with the polymer particle and comprises a fluorescent lanthanoid cation,
• wherein:
• a hydrophilic polymer which forms the hydrophilic shell comprises at least one hydrophilic macromonomer selected from the group consisting of a hydrophilic (meth)acryl macromonomer and a hydrophilic vinylamine macromonomer, and a hydrophobic polymer which forms the hydrophobic core is bonded to one terminal of a main chain of the hydrophilic macromonomer,
• a volume-average particle size of the fluorescent polymer particle is in a range of 0.01 to 20 μm, and
• the fluorescent lanthanoid dye comprises a nitrogen-containing heterocyclic ligand represented by the following Formula (L-I):
• Formula (L-I)
• wherein each of A21, A22 , and A23 is the same as or different from each other and represents an atomic group represented by any one of the following Formulae (L-II) to (L-V), a hydroxyl group, an alkoxy group, an aryloxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group;
• each of B21 and B22 independently represents a nitrogen atom or ═C(—R30)—;
• and R30 represents a hydrogen atom or a substituent:
• wherein each of R21 to R29 independently represents a hydrogen atom or a substituent;
• R27 and R28, R28 and R29 and/or R27 and R29 are optionally bonded with each other to form a ring;
• n represents an integer of 0, 1 or 2;
• G represents a substituted or unsubstituted carbon atom or a nitrogen atom;
• Q represents an atomic group which is used to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring which optionally forms a condensed ring;
• Ar21 represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring;
• and # represents a site to be bonded with the nitrogen-containing heterocycle in the ligand represented by Formula (L-I).

A method for forming a fluorescent polymer fine particle having a core-shell configuration comprising a hydrophobic core and a hydrophilic shell and a fluorescent lanthanoid dye that is integrated with the polymer particle and comprises a fluorescent lanthanoid cation, wherein a volume-average particle size of the fluorescent polymer particle is in the range of 0.01 to 20 μm, comprising:

• dispersing and polymerizing a hydrophobic radical polymerizable monomer in an aqueous solvent in the presence of a radical generator and the presence of a hydrophilic polymer precursor comprising a polymerizable unit and at least one hydrophilic unit selected from the group consisting of a hydrophilic (meth)acrylamide unit and a hydrophilic vinyl amine unit so that the polymer fine particle have the core-shell configuration in which a hydrophobic polymer which forms the hydrophobic core is bonded to a hydrophilic polymer which forms the hydrophilic shell;
• and
• introducing the fluorescent lanthanoid dye with the polymer particle,
• wherein the fluorescent lanthanoid dye comprises a nitrogen-containing heterocyclic ligand represented by the following Formula (L-I):
• Formula (L-I)
• wherein each of A21, A22, and A23 is the same as or different from each other and represents an atomic group represented by any one of the following Formulae (L-II) to (L-V), a hydroxyl group, an alkoxy group, an aryloxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group;
• each of B21 and B22 independently represents a nitrogen atom or ═C(—R30)—;
• and R30 represents a hydrogen atom or a substituent:
• wherein each of R21 to R29 independently represents a hydrogen atom or a substituent;
• R27 and R28, R28 and R29 and/or R27 and R29 are optionally bonded with each other to form a ring;
• n represents an integer of 0, 1 or 2;
• G represents a substituted or unsubstituted carbon atom or a nitrogen atom;
• Q represents an atomic group which is used to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring which optionally forms a condensed ring;
• Ar21 represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring;
• and # represents a site to be bonded with the nitrogen-containing heterocycle in the ligand represented by Formula (L-I).

A method for forming a fluorescent polymer fine particle having a core-shell configuration comprising a hydrophobic core and a hydrophilic shell and a fluorescent lanthanoid dye that is integrated with the polymer particle and comprises a fluorescent lanthanoid cation, wherein a volume-average particle size of the fluorescent polymer particle is in a range of 0.01 to 20 μm, comprising:

• dispersing and polymerizing a hydrophobic radical polymerizable monomer in an aqueous solvent in the presence of a radical generator and the presence of at least one hydrophilic macromonomer selected from the group consisting of a hydrophilic (meth)acryl macromonomer having a polymerizable double bond at one terminal end of the main chain thereof and a hydrophilic vinylamine macromonomer having a polymerizable double bond at one terminal end of the main chain thereof so that the polymer fine particle have the core-shell configuration in which a hydrophobic polymer which forms the hydrophobic core is bonded to a hydrophilic polymer which forms the hydrophilic shell;
• and
• introducing the fluorescent lanthanoid dye with the polymer particle,
• wherein the fluorescent lanthanoid dye comprises a nitrogen-containing heterocyclic ligand represented by the following Formula (L-I):
• Formula (L-I)
• wherein each of A21, A22, and A23 is the same as or different from each other and represents an atomic group represented by any one of the following Formulae (L-II) to (L-V), a hydroxyl group, an alkoxy group, an aryloxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group;
• each of B21 and B22 independently represents a nitrogen atom or ═C(—R30)—;
• and R30 represents a hydrogen atom or a substituent:
• wherein each of R21 to R29 independently represents a hydrogen atom or a substituent;
• R27 and R28, R28 and R29 and/or R27 and R29 are optionally bonded with each other to form a ring;
• n represents an integer of 0, 1 or 2;
• G represents a substituted or unsubstituted carbon atom or a nitrogen atom;
• Q represents an atomic group which is used to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring which optionally forms a condensed ring;
• Ar21 represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring;
• and # represents a site to be bonded with the nitrogen-containing heterocycle in the ligand represented by Formula (L-I).

A complex for detecting fluorescence comprising a fluorescent polymer fine particle and a combination substance capable of being combined with a target substance to be detected, wherein the fluorescent polymer fine particle comprises:

• a polymer particle having a core-shell configuration comprising a hydrophobic core and a hydrophilic shell;
• and
• a fluorescent lanthanoid dye that is integrated with the polymer particle and comprises a fluorescent lanthanoid cation,
• wherein:
• a hydrophilic polymer which forms the hydrophilic shell comprises a polymerizable unit and at least one hydrophilic unit selected from the group consisting of a hydrophilic (meth)acrylamide unit and a hydrophilic vinyl amine unit,
• a volume-average particle size of the fluorescent polymer particle is in a range of 0.01 to 20 μm, and
• the fluorescent lanthanoid dye comprises a nitrogen-containing heterocyclic ligand represented by the following Formula (L-I):
• Formula (L-I)
• wherein each of A21, A22, and A23 is the same as or different from each other and represents an atomic group represented by any one of the following Formulae (L-II) to (L-V), a hydroxyl group, an alkoxy group, an aryloxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group;
• each of B21 and B22 independently represents a nitrogen atom or ═C(—R30)—;
• and R30 represents a hydrogen atom or a substituent:
• wherein each of R21 to R29 independently represents a hydrogen atom or a substituent;
• R27 and R28, R28 and R29 and/or R27 and R29 are optionally bonded with each other to form a ring;
• n represents an integer of 0, 1 or 2;
• G represents a substituted or unsubstituted carbon atom or a nitrogen atom;
• Q represents an atomic group which is used to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring which optionally forms a condensed ring;
• Ar21 represents an aromatic hydrocarbon ring or an aromatic hydrocarbon ring or an aromatic heterocyclic ring;
• and # represents a site to be bonded with the nitrogen-containing heterocycle in the ligand represented by Formula (L-I).

A method for detecting fluorescence comprising detecting a detection target substance by using a fluorescent polymer fine particle and a combination substance capable of being combined with the target, wherein the fluorescent polymer fine particle comprises:

• a polymer particle having a core-shell configuration comprising a hydrophobic core and a hydrophilic shell;
• and
• a fluorescent lanthanoid dye that is integrated with the polymer particle and comprises a fluorescent lanthanoid cation,
• wherein:
• a hydrophilic polymer which forms the hydrophilic shell comprises a polymerizable unit and at least one hydrophilic unit selected from the group consisting of a hydrophilic (meth)acrylamide unit and a hydrophilic vinyl amine unit,
• a volume-average particle size of the fluorescent polymer particle is in a range of 0.01 to 20 μm, and
• the fluorescent lanthanoid dye comprises a nitrogen-containing heterocyclic ligand represented by the following Formula (L-I):
• Formula (L-I)
• wherein each of A21, A22, and A23 is the same as or different from each other and represents an atomic group represented by any one of the following Formulae (L-II) to (L-V), a hydroxyl group, an alkoxy group, an aryloxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group;
• each of B21 and B22 independently represents a nitrogen atom or ═C(—R30)—;
• and R30 represents a hydrogen atom or a substituent:
• wherein each of R21 to R29 independently represents a hydrogen atom or a substituent;
• R27 and R28, R28 and R29 and/or R27 and R29 are optionally bonded with each other to form a ring;
• n represents an integer of 0, 1 or 2;
• G represents a substituted or unsubstituted carbon atom or a nitrogen atom;
• Q represents an atomic group which is used to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring which optionally forms a condensed ring;
• Ar21 represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring;
• and # represents a site to be bonded with the nitrogen-containing heterocycle in the ligand represented by Formula (L-I).

A kit for detecting fluorescence comprising a fluorescent polymer fine particle, wherein the fluorescent polymer fine particle comprises:

• a polymer particle having a core-shell configuration comprising a hydrophobic core and a hydrophilic shell;
• and
• a fluorescent lanthanoid dye that is integrated with the polymer particle and comprises a fluorescent lanthanoid cation,
• wherein:
• a hydrophilic polymer which forms the hydrophilic shell comprises a polymerizable unit and at least one hydrophilic unit selected from the group consisting of a hydrophilic (meth)acrylamide unit and a hydrophilic vinyl amine unit,
• a volume-average particle size of the fluorescent polymer particle is in a range of 0.01 to 20 μm, and
• the fluorescent lanthanoid dye comprises a nitrogen-containing heterocyclic ligand represented by the following Formula (L-I):
• Formula (L-I)
• wherein each of A21, A22, and A23 is the same as or different from each other and represents an atomic group represented by any one of the following Formulae (L-II) to (L-V), a hydroxyl group, an alkoxy group, an aryloxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group;
• each of B21 and B22 independently represents a nitrogen atom or ═C(—R30)—;
• and R30 represents a hydrogen atom or a substituent:
• wherein each of R21 to R29 independently represents a hydrogen atom or a substituent;
• R27 and R28, R28 and R29 and/or R27 and R29 are optionally bonded with each other to form a ring;
• n represents an integer of 0, 1 or 2;
• G represents a substituted or unsubstituted carbon atom or a nitrogen atom;
• Q represents an atomic group which is used to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring which optionally forms a condensed ring;
• Ar21 represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring;
• and # represents a site to be bonded with the nitrogen-containing heterocycle in the ligand represented by Formula (L-I).