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. 2020 Mar 16;25(6):1347. doi: 10.3390/molecules25061347

Table 4.

Methods for quantitative determination of quinolones based on complexation with lanthanides.

Quinolone Method (System, Optimum pH, Optimum Buffer Conditions) λexitation/λemission Limit of Detection/Limit ofQuantification (LOD/LOQ) Matrix Ref
Balofloxacin (BLFX) BLFX-Eu3+-SDBS system;
pH = 7.5-tris HCl buffer;		 335 nm/618 nm LOD = 5 nM Serum and urine samples [111]
BLFX-Eu3+-SDBS system;
pH = 7.5-tris HCl buffer;		 335 nm/618 nm LOD = 1.3 nM Bile Acid [112]
BLFX-Eu3+-KBrO3-Na2S2O4-SDBS chemiluminescence system CL excitation/593 nm,
617 nm		 LOD = 0.069 nM Pharma-ceutical formulations and biological fluids [113]
BLFX-Eu3+-Y3+-SDBS system 330 nm/618 nm LOD = 0.83 nM Pharma-ceutical formulations, human serum, urine [114]
Ciprofloxacin (CPX) CPX-Tb.+3-TOPO system
pH = 5.5-acetate buffer; micellar solution of CPCl		 333 nm/546 nm LOD = 1.2 nM Serum samples [85]
CPX-Tb3+-SLS system;
pH = 6- acetic acid- sodium acetate buffer;		 300-325 nm / 549nm LOD = 30–150 mol/kg Chicken and trout muscle sample [115]
CPX-Ad/Tb3+ CPNP nanoparticles;
pH = 7.5-HEPES buffer;		 288 nm/545 nm LOD = 60 nM Aqueous solution, urine, tablets [92]
CPX-Tb3+-DO3A NPs;
pH = 7.4-HEPES buffer;		 278 nm/542 nm LOD = 9 nM Urine [84]
CPX-Tb3+-TOPO system;
pH = 6-piperazine andimidazole buffer;		 320 nm/545 nm LOD = 100 nM LC eluent [116]
CPX-Tb3+ system;
pH = 5.7-potassium hydrogen phthalate buffer;
(Additionally applied for: enrofloxacin and flumequine)		 337 nm/545 nm LOD = 9.6 nM Water samples [117]
CPX-Tb3+-SDS-Na2SO3 system;
pH = 6.5-acetate buffer;		 271 nm/545 nm; LOD = 1810.7 nM Serum samples [108]
CPX-Tb3+-CTAB system;
pH = 7.3-Tris buffer;
in the presence of tetracycline.		 284 nm/545 nm LOD = 27162 nM Serum and urine samples [118]
CPX-Tb3+ -SDS system;
pH = 5.7-sodium acetate buffer;		 278 nm/545 nm. LOD = 422.5 nM;
LOQ = 1508.9 nM.		 Milk samples [86]
CPX-Tb3+-CeIV–SO32-
chemiluminescence system		 CL excitation/ 490 nm, 545 nm,
585 nm 620 nm		 LOD = 0.31 nM Capsules, human serum and urine samples [119]
CPX- [Tb(bpy)2]3+–K2S2O8;
pH = 5.5- acetic acid– sodium acetate buffer		 ECL excitation/ 490 nm, 545 nm,
585 nm 620 nm		 LOD = 1.4 nM Pharma-ceutical tablets [120]
CPX- Tb3+-calf thymus DNA;
pH = 5.5- acetic acid– sodium acetate buffer		 272 nm/545 nm LOD = 37.9 nM eye-ear pharma-ceutical dosage forms [121]
CPX-Eu3+-phen system;
pH = 9-acetate-ammonia buffer; micellar solution of DDBS.		 330 nm/615 nm LOD = 230 nM Pharma-ceutical tablets, blood serum [91]
CPX-Eu3+-GMP NPs;
pH = 7.4-HEPES buffer;		 276 nm/615 nm LOD = 780 nM Pharma-ceutical tablets [94]
CPX-Eu3+ system in acetonitrile;
pH = 6-borate buffer;		 365 nm/615 nm LOD = 15 nM;LOQ = 45 nM Pharma-ceutical tablets, serum [122]
CPX-Eu3+-Ag NPs;
pH = 9.4-tris-HCl buffer		 373 nm/614 nm LOD = 0.057 nM Pharma-ceutical tablets, serum [123]
CPX-Eu3+ functionalized Ga(OH)(btec)·0.5H2O, where H4btec = 1,2,4,5-benzenetetra-carboxylic acid 370 nm/614 nm LOD = 7243 nM Urine samples [124]
Danofloxacin (DAN) DAN-Tb3+-SDS-Na2SO3 system;
pH = 6.5-acetate buffer;		 271 nm/545 nm; LOD = 1810.7 nM Serum samples [108]
Enoxacin (ENX) ENX-Dy3+-Ce4+-S2O32--H2SO4 system;
(Additionally applied for: lomefloxacin, ofloxacin, norfloxacin, gatifloxacin)		 CL excitation/482 nm,
578 nm		 LOD = 624.3 nM Biological fluids [109]
ENX- Dy3+- MnO4-- S2O32- -HNO3 system; CL excitation / 482 nm,
578 nm		 LOD = 686.8 nM Biological fluids [125]
ENX-Tb3+-Na2SO3 system;
pH = 7		 ECL excitation /490 nm,
545 nm,
585 nm,
620 nm.		 LOD = 0.054 nM Dosage forms, urine samples. [106]
ENX-Tb3+-KMnO4-Na2SO3
(Additionally applied for ofloxacin)		 CL excitation /490 nm,
545 nm,
585 nm,
620 nm.		 LOD = 0.24 nM Dosage forms, urine sample [126]
ENX-Tb3+- acetylacetone NPs
pH = 7.2, phosphate buffer		 345 nm/559 nm
(FRET method)		 LOD = 30 nM Dosage forms, urine sample [127]
Enrofloxacin (EF) EF-Eu3+-phen system;
pH = 9- acetate-ammonia buffer; micellar solution of DDBS.		 330 nm/615 nm LOD = 230 nM Blood sample [91]
EF-Eu3+-optical sensor
pH = 7.8		 395 nm/617 nm LOD = 75 nM Pharma-ceutical tablets and serum samples [128]
EF-Eu3+-polymer nanofilament-based
optical sensor
pH = 7.5, HEPES buffer		 340 nm/612 nm LOD = 580 nM Water-rich media [129]
EF-Tb3+-SLS system;
pH = 6-acetic acid-sodium acetate buffer;		 300 nm-
325 nm/549 nm		 LOD = 5.56 nM Chicken and trout muscle sample [115]
EF-Tb3+-Ag NPs
pH = 6, Tris–HCl buffer		 327 nm/545 nm LOD = 58.4 nM
LOQ = 191.9 nM		 Milk samples [130]
EF-Tb3+-Fe(II)/(III)-H2O2
EF-Tb3+-KNO2-H2O2
(Additionally applied for levofloxacin and pefloxacin)		 CL excitation/440 nm
515 nm		 LOD = 120 nM
LOD = 240 nM		 Pharma-ceutical forms and urine samples [131]
EF-Tb3+-calf thymus DNA
pH = 6.5-hexamethylenetetramine buffer		 324 nm/ 546 nm LOD = 6.95 nM Beef serum [132]
Fleroxacin (FLX) FLX-Dy3+-MnO4−-S2O32−-H6P4O13 system;
(Additionally applied for pefloxacin and pipemidic acid)		 CL excitation/482 nm,
578 nm		 LOD = 0.812 nM Foods, biological samples [104]
FLX-Dy3+-KMnO4-Na2S2O3-H6P4O13 CL excitation/482 nm,
578 nm		 LOD = 0.3 nM Injections and urine sample [133]
FLX-Eu3+-[(Me)4N]2[Pb6K6(m-BDC)9(OH)2]·H2O, where 1,3-H2BDC = 1,3-benzenedicarboxylic acid) 377 nm/612 nm LOD = 118.8 nM Human serum and urine [134]
FLX-Tb3+ photochemical fluorimetric system
pH = 5.7, acetate buffer		 320 nm/545 nm LOD = 12 nM Human urine samples [135]
Flumequine (FLU) FLU-Tb3+ Ce4+-Na2SO3-H2SO4
system;		 Excitation by redox reaction/- LOD = 382.7 nM;
LOQ = 1148.1 nM;		 Waste water samples [105]
FLU-Tb3+-SDS micelles system;
pH = 7.6-Tris buffer;		 340 nm/545 nm LOD = 210.5 nM Chicken muscle and liver, whole milk. [136]
FLU-Tb3+-1,10-phenanthroline in
micellar SDS solutions
pH = 7.5-acetate-ammonia buffer		 330 nm/545 nm LOD = 4.9 nM Chicken meat [137]
FLU-Eu3+-Tb3+-nanocomposites
pH = 6.9 acetic acid buffered with ammonia		 255 nm/360 nm LOD = 4.6 nM Meat samples [138]
Garenoxacin (GAR) GAR-Tb3+-SDS micelles-Na2SO3 system;
pH = 4.1-acetate buffer;		 281 nm/546 nm LOD = 46.9 nM;
LOQ = 152.4 nM		 Serum and urine samples [89]
Gatifloxacin (GFLX) GFLX- Eu3+ system in acetonitrile;
pH = 3.5- acetate buffer;		 395 nm/617 nm LOD = 16 nM;
LOQ = 28 nM		 Pharma-
ceutical tablets, serum.		 [122]
GFLX-Eu3+-SDBS system
pH = 7.5-Tris–HCl buffer		 338 nm/617 nm LOD = 1 nM Injections and human urine/serum samples [139]
GFLX-Eu3+ system in sol- gel matrix;
pH = 6 - borate buffer;		 370 nm/617 nm; LOD = 0.16 nM Pharma-
ceutical and serum samples.		 [140]
GFLX-Tb3+ system in sol-gel matrix;
pH = 3.5-acetate buffer;		 350 nm/545 nm; LOD = 20 nM Pharma-
ceutical and serum samples.		 [140]
Grepafloxacin (GREP) GREP-Tb3+-SDS micellar solution system;
pH = 6-acetate buffer;		 275 nm/546 nm LOD = 27824.5 nM;
LOQ = 83473.5 nM		 Human serum and urine [88]
GREP-Tb3+-Ce(IV)–Na2SO3
pH = 4-15mM sodium dodecyl sulphate solution		 280 nm/450 nm LOD = 27.8 nM Pharmaceutical tablets and human urine [141]
Levofloxacin (LEVO) LEVO-Tb3+ system; micellar solution of SDS;
pH = 6-acetate buffer;		 292 nm/546 nm LOD = 27672.6 nM;
LOQ = 83017.8 nM		 Pharma-
ceutical tablets, human serum, urine.		 [87]
LEVO-Tb3+ system; colloidal silver NPs;
pH = 9-tris-HCl buffer;		 284 nm/545 nm LOD = 7.19x10-9 nM Serum samples, urine [95]
LEVO-Tb3+-gold NPs system;
pH = 6.8 NaH2PO4/Na2HPO4 buffer;		 373 nm/545 nm LOD = 0.21 nM;
LOQ = 0.72 nM		 Powder, tablets. [99]
LEVO-Sm3+ system;
pH = 6-acetate buffer;		 312 nm/553 nm LOD = 52.5 nM;
LOQ = 154.7 nM		 Powder,
tablets		 [142]
LEVO-Eu3+-Ce4+-SO32−-H2SO4 system;
(Additionally applied for moxifloxacin and trovafloxacin)		 - LOD = 276.7 nM;
LOQ = 968.45 nM		 Tablets [110]
LEVO-Eu3+-covalent
organic framework-based hybrid material		 380 nm/613 nm LOD = 200 nM Serum and urine samples [143]
LEVO-Ce(IV) in micellar solutions of of cetyltrimethyl ammonium bromide 250 nm/355 nm
(FRET method)		 - Injections [144]
Lomefloxacin (LOM) LOM-Sm3+ system;
pH = 6- acetate buffer;		 310 nm/556 nm LOD = 65.4 nM;
LOQ = 199 nM		 Powder, tablets. [142]
LOM-Tb3+-silver NPs system;
pH = 6-acetate buffer;		 274 nm/545 nm LOD = 0.11 nM; Tablets, serum, urine samples. [98]
LOM-Tb3+-Ce(IV)-Na2SO3
pH = 2-H2SO4 		CL excitation/490 nm,
545 nm,
585 nm,
620 nm		 LOD = 1.1 nM Pharmaceutical tablets, urine and serum samples [145]
Marbofloxacin (MAR) MAR-Tb3+ system;
pH = 6.0-acetic acid/ ammonium acetate buffer;
(Additionally applied for: ciprofloxacin, danofloxacin, enrofloxacin, sarafloxacin, difloxacin, oxolinic acid, flumequine)		 FL: 340 nm/545 nm;
TR: 281 nm/545 nm		 LOD = 165.56 nM (FL);
LOD = 262.17 nM (TR);		 Whole, semi-skimmed, skimmed milk. [146]
MAR-Tb4O7 NPs-TOPO-SDS-hexamine system;
pH = 7.0–7.5-Tris buffer;
(Applied also for: ciprofloxacin, danofloxacin, enrofloxacin, sarafloxacin, oxolinic acid, fumequine).		 340 nm/545 nm. LOD = 96.59 nM
 Skimmed, semi-
skimmed, whole milk samples.		 [97]
Moxifloxacin (MOXI) MOXI-Tb3+ system; colloidal silver NPs;
pH = 9-Tris-HCl buffer;		 284 nm/545 nm LOD = 8.47 × 10−9 nM Serum samples, urine [95]
Norfloxacin (NOR) NOR-Tb3+ -TOPO system
pH = 5.5- acetate buffer; micellar solution of CPCl		 333 nm/490 nm LOD = 1.7 nM Serum samples [85]
Marbofloxacin (MAR) MAR-Tb3+ system;
pH = 6.0-acetic acid/ ammonium acetate buffer;
(Additionally applied for: ciprofloxacin, danofloxacin, enrofloxacin, sarafloxacin, difloxacin, oxolinic acid, flumequine)		 FL: 340 nm/545 nm;
TR: 281 nm/ 545 nm		 LOD = 165.56 nM (FL);
LOD = 262.17 nM (TR);		 Whole, semi-skimmed, skimmed milk. [146]
MAR-Tb4O7 NPs-TOPO-SDS-hexamine system;
pH = 7.0–7.5-Tris buffer;
(Applied also for: ciprofloxacin, danofloxacin, enrofloxacin, sarafloxacin, oxolinic acid, fumequine).		 340 nm/545 nm. LOD = 96.59 nM Skimmed, semi-skimmed, whole milk samples. [97]
Moxifloxacin (MOXI) MOXI-Tb3+ system; colloidal silver NPs;
pH = 9-Tris-HCl buffer;		 284 nm/545 nm LOD = 8.47 × 10−9 nM Serum samples, urine [95]
Norfloxacin (NOR) NOR-Tb3+-TOPO system
pH = 5.5-acetate buffer; micellar solution of CPCl		 333 nm/490 nm LOD = 1.7 nM Serum samples [85]
NOR-Tb3+-calf thymus DNA;
pH = 5.5-acetic acid–sodium acetate buffer		 272 nm/545 nm LOD = 35.8 nM Eye-ear pharma-ceutical dosage forms [121]
NOR-Tb3+-zeolite of the CaA-type
pH = 7-buffered with a 40% aqueous solution of urothropine
(Additionally applied for ciprofloxacin)		 365 nm/545 nm LOD = 3131 nM Urine and human plasma samples [147]
NOR-Tb3+-Na2SO3 system
pH = 7		 ECL excitation/490 nm,
545 nm,
585 nm,
620 nm		 LOD = 0.028 nM Pharmaceutical capsules, urine samples [148]
NOR-Sm3+ system;
pH = 6-acetate buffer;		 314 nm/553 nm LOD = 84.5 nM;
LOQ = 253.6 nM;		 Powder, tablets [142]
NOR-Tb3+ sodium tetradecylsulfate system;
pH = 7–8;		 337 nm/545 nm LOD = 0.0031 nM Used in HELC [149]
NOR-Ce4+ system;
Acidic pH-perchloric acid 0.02-0.08 mol/L;		 -/550 nm LOD = 31.3 nM;
LOQ = 93.9 nM		 Pharma-ceutical capsules, eye drops, urine [100]
NOR-Tb3+(bipy)2
(DPA)-K2S2O8 system;
pH = 10-NaBO4-NaOH buffer;		 ECL excitation /485 nm,
545 nm,
582 nm,
621 nm		 LOD = 0.69 nM Urine samples [101]
NOR- PEG coated Tb3+ doped ZnS NPs system;
pH = 7.6-tris-HCl buffer;		 334 nm/491 nm,
545 nm		 LOD = 0.05 nM;
LOQ = 0.17 nM		 Eye drops, urine samples [96]
NOR-Tb3+ system flow through solid phase system;
pH = 5.6-acetate buffer;		 273 nm/545 nm. LOD = 4.7 nM;
LOQ = 15.7 nM		 Serum and urine samples. [150]
NOR-Tb3+-KMnO4 -Na2SO3 system-optical flow-through sensor;
pH = 3-KH phthalate-HCl buffer;		 CL excitation/545 nm LOD = 8.7 nM Pharma-ceutical samples [102]
NOR-AMP-Tb3+ CPNSs system;
pH = 7.5;
(Additionally applied for: pefloxacin, sparfloxacin, fleroxacin, nalidixic acid as well.)		 280 nm/545 nm LOD = 10 nM Milk [93]
NOR-Tb3+-SDS-Na2SO3 system;
pH = 6.5-acetate buffer;		 271 nm/545 nm; LOD = 1.88 nM Serum samples. [108]
NOR-Tb3+ system in sol-gel matrix;
pH = 3.5-acetate buffer;		 395 nm/545 nm; LOD = 10 nM Pharma-ceutical and serum samples. [140]
NOR- Eu3+ system in sol-gel matrix;
pH = 6- borate buffer;		 340 nm/617 nm; LOD = 3.0 nM Pharma-ceutical and serum samples. [140]
NOR fluorescence immunoassay coating-antigen-modified polystyrene particles - anti-norfloxacin monoclonal
antibody conjugated with carboxyl-functionalized
NaYF4:Yb,Er upconversion NPs
pH = 7.4-phosphate-buffered saline		 980 nm/542 nm LOD = 0.03 nM Milk, chicken, pork kidney samples [151]
Ofloxacin (OFLO) OFLO-Tb3+-TTDC;
pH = 7–8;		 337 nm/545 nm LOD = 0.0000276 nM Used in HELC [149]
Ce4+-Na2SO3-OFLO-Tb3+ system;
Acidic pH- HCl.
Flow-injection coupled with CL detection		 - LOD = 20.75 nM Plasma samples [152]
OFLO-Ru(bipy)2(CIP)2+
Ce4+ system;
Acidic pH -HNO3 		CL excitation / 617 nm,
624 nm		 LOD = 4.2 nM Pharma-ceutical samples, urine samples [103]
OFLO-Eu3+ system;
pH = 5.1- acetate buffer.		 365 nm/617 nm LOD = 3 nM;
LOQ = 9 nM		 Pharma-ceutical and serum samples [153]
OFLO-Tb3+-Na2SO3 system;
pH = 7;		 ECL excitation /490 nm,
545 nm,
585 nm,
620 nm.		 LOD = 0.16 nM Dosage forms, urine samples. [106]
Orbifloxacin (ORBI) ORBI-Tb3+ system;
pH = 6-acetate buffer;		 275 nm/545 nm LOD = 8.35 nM;
LOQ = 25.3 nM		 Tablets,
urine samples
 [154]
Pazufloxacin (PAZ) PAZ- Tb3+ system;
pH = 6.3- acetate buffer;		 330 nm/545 nm LOD = 6.2 nM Serum and urine samples [155]
PAZ-Eu3+-KMnO4-
Na2S2O4 system;
pH = 6.		 CL excitation/592 nm,
617 nm,
695 nm.		 LOD = 2.6 nM Serum and urine samples. [156]
PAZ- Ce4+- Na2SO3- H2SO4 system; -/ 247 nm LOD = 2.2 nM Urine samples [157]
Pefloxacin (PEF) PEF-Tb3+-TOPO system;
pH = 5.5-acetate buffer; micellar solution of CPCl		 333 nm/590 nm LOD = 4.4 nM Serum samples [85]
PEF-Tb3+- KMnO4/ H2SO3 system;
Acidic pH-H2SO4;		 CL excitation /543 nm LOD = 41.1 nM Semi-skimmed milk samples [107]
PEF-Tb3+-Ag NPs
pH = 6-acetate buffer		 273 nm/545 nm LOD = 25 nM Pharmaceutical capsules and serum samples [158]
Pipemidic acid (PPA) PPA-Tb3+-Ag+ NPs system;
pH = 6-acetate buffer;		 320 nm/545 nm. LOD = 0.047 nM Tablets, serum, urine samples. [98]
PPA-Tb3+ system;
pH = 5.6- acetate buffer;		 320 nm/545 nm. LOD = 5.9 nM Urine and serum samples [159]
Prulifloxacin (PUFX) PUFX-Tb3+-KMnO4-Na2S2O4 system;
pH = 5.8;
(Additionally applied for ulifloxacin –pH = 5.4)		 CL excitation/490 nm,
545 nm,
585 nm,
620 nm.		 LOD = 7 nM Tablets [160]
PUFX-Tb3+-KMnO4-Na2SO3
KH2PO4-NaOH buffer		 275 nm/423 nm LOD = 8 nM Pharmaceutical tablets, serum, and urine samples [161]
Ulifloxacin (UFX) UFX-Eu3+-SDBS system;
pH = 8.6-NH4Cl/NH3x H2O buffer;		 276 nm/616 nm. LOD = 0.2 nM Human serum and urine [162]

LOD = limit of detection; LOQ = limit of quantification; Ad = adenine; AMP = adenosine monophosphate; Bipy = 2,2′-bipyridyl; CIP = 4-carboxyl-imidazole [4,5-f] [1,10]-phenanthroline; DPA = 2,6-pyridinedicarbocylic acid; CPCl = cetylpiridinium chloride; CL = chemiluminescence; ECL = electrochemiluminescence; NPs = nanoparticles; CPNPs = coordination polymer nanoparticles; CPNSs = coordination polymer nanosheets; CTAB = cetyltrimethylammonium bromide; DDBS = sodium dodecyl-benzensulfonate; DO3A = 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid; FL = fluorescence; TR = time-resolved fluorescence; GMP = guanosine-5-monophosphate; HELC = high-efficiency liquid chromatography; HEPES = N-2-hydroxyethyl piperazine-N′-2-ethanesulfonic acid; Phen = 1,10-phenanthroline; SDS = sodium dodecyl sulphate; SDBS = sodium dodecylbenzene sulfonate; SLS = sodium laurylsulphate; TOPO = tri-n-octylphosphine oxide; TTDC = sodium tetradecylsulfate; FRET = fluorescence resonance energy transfer.