Flow-injection chemiluminescence study of Ce(IV)-Na2SO3-Tb(III)-fluoquinolone antibiotic system with DNA

A novel flow injection chemiluminescence (CL) system is developed to determine DNA. According to the fact that DNA linearly quenches the CL intensity of Ce(IV)-Na(2)SO(3)-Tb(III)-fluoquinolone antibiotic (FLUQ) system, DNA concentration is determined. The calibration graphs are linear in the range of 0.04-10 microg/ml (for both natural and denatured DNA), and the 3sigma limits of detection are 7.8 ng/ml (natural DNA) and 9.5 ng/ml (denatured DNA). According to fluorescence spectrum and CL spectrum, and through studying the reaction of Ce(IV)-Na(2)SO(3)-Tb(III)-FLUQ with nucleotides and bases, we conclude that DNA counteracts the energy transfer from FLUQ to Tb(III), and this function is related to both bases and phosphate groups in DNA.     

高效液相色谱-柱后化学发光法检测人体尿液中的卡托普利

在酸性条件下,Ce?氧化Ru(bipy)32+生成Ru(bipy)33+,同时氧化卡托普利生成二硫化物中间活性态([RS-SR]*),Ru(bipy)33+和二硫化物中间活性态之间相互反应产生强烈的化学发光。基于此,根据发光试剂Ru(bipy)32+水溶性好、试剂稳定等特点,将其加入到流动相中,通过高效液相色谱分离,建立了柱后化学发光快速灵敏检测卡托普利的方法。在以甲醇-0.01mol/L KH2PO4-1g/L Ru(bipy)32+(80∶20∶2,V/V)为流动相,流速为0.9mL/min,8.0×10-4 mol/L Ce?的优化实验条件下,方法的线性范围为2.0×10-7～1.0×10-4 mol/L(R2=0.9988),检出限为6.0×10-8 mol/L(S/N=3),并对1×10-5 mol/L卡托普利平行测定11次,相对标准偏差(RSD)为1.8%。将本方法用于人体尿液中卡托普利含量的测定,结果令人满意。结合化学发光光谱,对该体系发光机理进行了探讨。     

Flow-injection chemiluminescence determination of ofloxacin and levofloxacin in pharmaceutical preparations and biological fluids.

A novel, rapid and sensitive analytical method is described for determination of ofloxacin and levofloxacin by enhanced chemiluminescence (CL) with flow-injection sampling. The method is based on the CL reaction of the Ce(IV)-Na2S2O4-ofloxacin/levofloxacin-H2SO2 system. The enhanced CL mechanism was developed and the optimum conditions for CL emission were investigated. The CL intensity was correlated linearly (r = 0.9988) with the concentration of ofloxacin (or levofloxacin) in the range of 1.0 x 10(-8) - 1.0 x 10(-7) g ml(-1) and 1.0 x 10(-7) - 6.0 x 10(-6) g ml(-1). The detection limit (S/N = 3) is 7 x 10(-9) g ml(-1). The relative standard derivation (RSD, n = 11) is 2.0% for ofloxacin at 4 x 10(-7) g ml(-1) and for levofloxacin at 6 x 10(-7) g ml(-1). This method has been successfully applied for the determination of ofloxacin and levofloxacin in pharmaceutical preparations and biological fluids with satisfactory results.     

A simple and rapid flow-injection chemiluminescence method for the determination of noscapine with Ru(phen)3(2+)-Ce(IV) system

A new flow injection chemiluminescence (CL) system was used for the determination of noscapine. This technique is based on the reduction effect of noscapine on the Ru(phen)3(3+), which is produced by reaction between Ru(phen)3(2+) and acidic Ce(IV) solutions, and this rapid reduction produces strong CL. Calibration plots were linear over the range of 3.0 x 10(-7) - 2.0 x 10(-6) mol L(-1) and 2.0 x 10(-6) - 2.0 x 10(-4) mol L(-1). The CL intensity was so high, that it is able to produce a detection limit of 6.6 x 10(-8) M noscapine (3sigma). The relative standard deviation of 2.0 x 10(-6) M noscapine was 1.0% (n=10). The proposed method was successfully applied for the flow injection determination of noscapine in cough and Tonin syrup samples. The results of real sample analyses show good recovery percentages (97.3-102.4%). The minimum sampling rate was 100 samples per hour.     

A novel chemiluminescence technique for quantitative measurement of low concentration human serum albumin.

An efficient and highly sensitive chemiluminescence (CL) technique is proposed in the current study for detection of low levels of human serum albumin (HSA). Chemiluminescence (CL) produced during interaction between fluoresceinyl cypridina luciferin analog (FCLA)-1O2 can be modified with the presence of HSA. The conventional CL technique uses a quenching effect of HSA for its quantitative measurement. We are reporting here that the CL intensity can be enhanced, rather than quenched, by the addition of HSA. The CL signal can be linearly correlated with the HSA concentration over a clinically interesting range of 5 x 10(-9) - 8 x 10(-8) mol L(-1), with a detection limit of 2.5 x 10(-9) mol L(-1). The determination result was consistent with that obtained from conventional methods. One possible mechanism of HSA detection technique using CL enhancement approach is discussed. Intermolecular energy transfer in chemiluminescence systems and changes of microenvironment are likely to be contributors of the CL enhancement with HSA.     

Terbium sensitized determination of tosufloxacin using electrochemiluminescence method.

A novel method for determination of trace amounts of tosufloxacin (TFLX) based on electrochemiluminescence (ECL) has been developed. The calibration graphs for TFLX were linear in the range of 5.0 x 10(-11)-3.5 x 10(-7) mol/L, with the detection limit of 1.3 x 10(-11) mol/L. Key factors affecting the determination of TFLX were investigated. TFLX amounts in capsule and serum samples were successfully detected by this method. A possible mechanism of energy transfer, and thus the explanation of ECL in the Tb3+-TFLX-Na2S2O4 system are discussed.     

Fluorimetric study of the interaction between human serum albumin and quinolones-terbium complex and its application

A highly sensitive spectrofluorimetric method is proposed for determination of human serum albumin (HSA) and some quinolone drugs. Using quinolones-terbium (Tb3+) complex as a fluorescent probe, in the buffer solution of pH 7.8, HSA can remarkably enhance the fluorescence intensity of the quinolones-Tb3+ complex at 545 nm and the enhanced fluorescence intensity of Tb3+ ion is in proportion to the concentration of HSA and quinolone drugs. Optimum conditions for the determination of HSA were also investigated. The linear ranges and limits of detection are 8.0 x 10(-9) to 8.0 x 10(-8) mol L(-1), 4.20 x 10(-9) mol L(-1) (for HSA); 1.0 x 10(-6) to 4.0 x 10(-6) mol L(-1), 1.87 x 10(-8) mol L(-1) (for norfloxacin) and 1.0 x 10(-7) to 1.0 x 10(-6) mol L(-1), 4.82 x 10(-8) mol L(-1) (for enoxacine), respectively. This method is simple, practical and relatively free interference from coexisting substances, as well as much more sensitive than most of the existing assays.     

Titania sol–gel-derived tyrosinase-based amperometric biosensor for determination of phenolic compounds in water samples. Examination of interference effects

For detection of phenolic compounds in environmental water samples we propose an amperometric biosensor based on tyrosinase immobilized in titania sol-gel. The analytical characteristics toward catechol, p-cresol, phenol, p-chlorophenol, and p-methylcatechol were determined. The linear range for catechol determination was 2.2 x 10(-7)-1.3 x 10(-5) mol L(-1) with a limit of detection of 9 x 10(-8) mol L(-1) and sensitivity 2.0 x 10(3) mA mol(-1) L. The influence of sample matrix components on the electrode response was studied according to Plackett-Burman experimental design. The potential interferents Mg(2+), Ca(2+), HCO3(-), SO4(2-), and Cl(-), which are usually encountered in waters, were taken into account in the examination. Cu(2+) was also taken into account, because CuSO(4) is sometimes added to a water sample, as a preservative, before determination of phenolic compounds. It was found that among the ions tested only Mg(2+) and Ca(2+) did not directly affect the electrode response. The developed biosensor was used for determination of catechol in spring and surface water samples using the standard addition method.     

Photochemical fluorescence enhancement of the terbium-lomefloxacin complex and its application

The sensitized fluorescence intensity of the terbium ion (Tb(3+)) can be notably enhanced after the Tb(3+)-lomefloxacin(LFLX) complex system was irradiated by 365nm ultraviolet light. A photochemical reaction occurs to the irradiated Tb(3+)-LFLX complex. A new Tb(3+)system with intense fluorescence is obtained. On this basis a new sensitive and selective photochemical fluorimetry for the determination of LFLX was established. Under the optimal experimental conditions, the linear range of the determination is 2.0-500x10(-8) mol l(-1) for LFLX, and the detection limit is 6.0x10(-9) mol l(-1).Without any pre-treatment the recoveries of LFLX in human urine and serum were determined.     

Chemiluminescence of tryptophan and histidine in Ru(bpy)3(2+)-KMnO4 aqueous solution

Amino acids with different chemical structures have different abilities in terms of increasing the intensity of chemiluminescence (CL) of tris(2,2'-bipyridine)ruthenium(II) [Ru(bpy)3(2+)]. In a flow system, CL caused by the reaction between Ru(bpy)3(3+) and 15 amino acids was observed, but only tryptophan (Trp) and histidine (His) enhanced the intensity obviously, and so the CL of Trp and His and their molecular groups was studied. A calculation of the ionization potentials (IPs) of their N atom indicated that the CL intensities of these compounds depended on their IPs. In addition, the flow system was used for the determination of Trp and His, and the detection limits were 3 x 10(-8) mol L(-1) for His and 2.5 x 10(-9) mol L(-1) for Trp. The calibration curves for the two amino acids were 1.0 x 10(-7) to 5.0 x 10(-3) mol L(-1) for His and 1.0 x 10(-8) to 1.0 x 10(-4) mol L(-1) for Trp. The proposed approach was applied to the determination of His in Ganoderma.     

YF3:Ln3+ (Ln = Ce, Tb, Pr) submicrospindles: hydrothermal synthesis and luminescence properties

YF(3):Ln(3+) (Ln = Ce, Tb, Pr) microspindles were successfully fabricated by a facile hydrothermal method. X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), lifetimes, photoluminescence (PL) and low-voltage cathodoluminescence (CL) were used to characterize the resulting samples. The lengths and diameters of YF(3):0.02Ce(3+) microspindles are around 760 nm and 230 nm, respectively. Adding dilute acid and trisodium citrate (Cit(3-)) are essential for obtaining YF(3) microspindles. A potential formation mechanism for YF(3) microspindles has been presented. PL spectroscopy investigations show that YF(3):Ce(3+) and YF(3):Tb(3+) microcrystals exhibit the characteristic emission of Ce(3+) 5d → 4f and Tb(3+ 5)D(4)→(7)F(J) (J = 6-3) transitions, respectively. In addition, the energy transfer from Ce(3+) to Tb(3+) was investigated in detail for YF(3):Ce(3+), Tb(3+) microspindles. Under the excitation of electron beams, YF(3):Pr(3+) show quantum cutting emission and YF(3):Ce(3+), Tb(3+) phosphors exhibit more intense green emission than the commercial phosphor ZnO:Zn.     

Electrospinning synthesis and luminescence properties of one-dimensional La(9.33)(SiO4)6O2: Ln3+ (Ln = Ce, Eu, Tb) microfibers

One-dimensional La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) microfibers were fabricated by a simple and cost-effective electrospinning method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL) and low voltage cathodoluminescence (CL) as well as kinetic decay were used to characterize the resulting samples. SEM and TEM results indicated that the diameter of the microfibers annealed at 1000 °C for 3 h was 200-245 nm. The microfibers were further composed of fine and closely linked nanoparticles. La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) phosphors showed the characteristic emission of Ce(3+) (5d → 4f), Eu(3+) ((5)D(0)→(7)F(J)) and Tb(3+) ((5)D(3,4)→(7)F(J)) under ultraviolet excitation and low-voltage electron beams (3-5 kV) excitation. An energy transfer from Ce(3+) to Tb(3+) was observed in the La(9.33)(SiO(4))(6)O(2): Ce(3+), Tb(3+) phosphor under ultraviolet excitation and low-voltage electron beam excitation. Luminescence mechanisms were proposed to explain the observed phenomena. Blue, red and green emission can be realized in La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) microfibers by changing the doping ions. So the La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) phosphors have potential applications in full-color field emission displays.     

Luminescence and energy transfer in lu(3)al(5)o(12) scintillators co-doped with ce(3+) and tb(3+)

Lu(3)Al(5)O(12) (LuAG) doped with Ce(3+) is a promising scintillator material with a high density and a fast response time. The light output under X-ray or γ-ray excitation is, however, well below the theoretical limit. In this paper the influence of codoping with Tb(3+) is investigated with the aim to increase the light output. High resolution spectra of singly doped LuAG (with Ce(3+) or Tb(3+)) are reported and provide insight into the energy level structure of the two ions in LuAG. For Ce(3+) zero-phonon lines and vibronic structure are observed for the two lowest energy 5d bands and the Stokes' shift (2 350 cm(-1)) and Huang-Rhys coupling parameter (S = 9) have been determined. Tb(3+) 4f-5d transitions to the high spin (HS) and low spin (LS) states are observed (including a zero-phonon line and vibrational structure for the high spin state). The HS-LS splitting of 5400 cm(-1) is smaller than usually observed and is explained by a reduction of the 5d-4f exchange coupling parameter J by covalency. Upon replacing the smaller Lu(3+) ion with the larger Tb(3+) ion, the crystal field splitting for the lowest 5d states increases, causing the lowest 5d state to shift below the (5)D(4) state of Tb(3+) and allowing for efficient energy transfer from Tb(3+) to Ce(3+) down to the lowest temperatures. Luminescence decay measurements confirm efficient energy transfer from Tb(3+) to Ce(3+) and provide a qualitative understanding of the energy transfer process. Co-doping with Tb(3+) does not result in the desired increase in light output, and an explanation based on electron trapping in defects is discussed.     

Electrochemiluminescence of terbium (III)-two fluoroquinolones-sodium sulfite system in aqueous solution

The electrochemiluminescence (ECL) of Tb3+-enoxacin-Na2SO3 system (ENX system) and Tb3+-ofloxacin-Na2SO3 system (OFLX system) in aqueous solution is reported. ECL is generated by the oxidation of Na2SO3, which is enhanced by Tb3+-fluoroquinolone (FQ) complex. The ECL intensity peak versus potential corresponds to oxidation of Na2SO3, and the ECL emission spectra (the peaks are at 490, 545, 585 and 620 nm) match the characteristic emission spectrum of Tb3+, indicating that the emission is from the excited state of Tb3+. The mechanism of ECL is proposed and the difference of ECL intensity between ENX system and OFLX system is explained. Conditions for ECL emission were optimized. The linear range of ECL intensity versus concentrations of pharmaceuticals is 2.0 x 10(-10) -8.0 x 10(-7)mol l(-1) for ENX and 6.0 x 10(-10) -6.0 x 10(-7)mol l(-1) for OFLX, respectively. A theoretical limit of detection is 5.4 x 10(-11)mol l(-1) for ENX and 1.6 x 10(-10)mol l(-1) for OFLX, respectively. The ECL was satisfactorily applied to the determination of the two FQs in dosage form and urine sample.     

Spectrofluorometric determination of trace amounts of coenzyme II using norfioxacin-terbium complex as a fluorescent probe.

When terbium ion (Tb3+)-norfloxacin (NFLX) complex is issued a fluorescent probe, in a buffer solution of pH = 7.6, NADP can remarkably enhance the fluorescence intensity of the Tb3+ -NFLX complex at lambda = 545 nm. The enhanced fluorescence intensity of Tb3+ is in proportion to the concentration of NADP. The dynamic range for the determination of NADP is 1.11 x 10(-7) - 6.16 x 10(-5) mol l(-1), with a detection limit of 4.31 x 10(-8) mol l(-1). This method is simple, practical and relatively free of interference from coexisting substances, so it can be successfully applied to determination of NADP in synthetic water samples.     

On-line chemical generation of tris(2,2'-bipyridyl)ruthenium(III) and its application in CE with chemiluminescence detection

A novel tris(2,2'-bipyridyl)ruthenium(III) [Ru(bipy)(3) (3+)]-based chemiluminescence (CL) detection in CE using an on-line chemical generation scheme has been demonstrated. Two continuous streams respectively containing solutions of Ru(bipy)(3) (2+) and acidic cerium(IV) used as a homogeneous chemical oxidant are employed to generate Ru(bipy)(3) (3+), which is delivered into the reaction capillary of a coaxial flow interface and then reacted with analytes at the end of the separation capillary to yield light. The important operational parameters for separation and detection are identified and optimized. Four alpha-ketocarboxylic acids used as models, outside of the amine-containing compounds, are successfully separated and detected to evaluate the feasibility of the approach. The excellent resolution and detection sensitivity was achieved by using 50 mmol/L phosphate running buffer (pH 9.5) with 0.7 mmol/L CTAB, and CL reagent solution streams containing 0.15 mmol/L Ru(bipy)(3) (2+) and 0.8 mmol/L cerium(IV) (0.25 mol/L H(2)SO(4)), respectively. The concentration detection limits for alpha-ketocarboxylic acids were below 3.7x10(-8) mol/L (S/N = 3). The proposed method was applied to the determination of alpha-ketocarboxylic acids in five different honey samples with satisfactory results.     

Flow-injection chemiluminometric determination of some thioxanthene derivatives in pharmaceutical formulations and biological fluids using the [Ru(dipy)3(2+)]-Ce(IV) system.

A flow-injection (FI) methodology using tris(2,2'-dipyridyl)ruthenium(II), [Ru(dipy)3(2+)], chemiluminescence (CL) was developed for the rapid and sensitive determination of three thioxanthene derivatives, namely zuclopenthixol hydrochloride, flupentixol hydrochloride and thiothixene. The method is based on the CL reaction of the studied thioxanthenes with [Ru(dipy)3(2+)] and Ce(IV) in a sulfuric acid medium. Under the optimum conditions, calibration graphs were obtained over the concentration ranges 0.002-6 migrograms/ml for zuclopenthixol hydrochloride, 0.5-15 micrograms/ml for flupentixol hydrochloride and 0.05-7.5 micrograms/ml for thiothixene. The limits of detection (s/n = 3) were 4.2 x 10(-9) mol/l zuclopenthixol hydrochloride, 2 x 10(-8) mol/l flupentixol hydrochloride and 4.5 x 10(-8) mol/l thiothixene. The method was successfully applied to the determination of these compounds in dosage forms and biological fluids.     

Terbium-sensitized fluorescence method for the determination of pazufloxacin mesilate and its application.

A simple, rapid and highly sensitive fluorometric method for the determination of pazufloxacin mesilate (PZFX) is described. It is based on the formation of the complex [Tb(PZFX)2](3+), which shows the intensive characteristic bands of Tb3+. Optimum conditions for the determination were investigated. Under the optimum experimental condition, the fluorescence intensity responds linearly to the PZFX concentration in the range of 2.0 x 10(-8) - 5.0 x 10(-6) mol/l with a detection limit of 6.2 x 10(-9) mol/l. The method has been successfully applied to the determination of PZFX in urine and serum samples.     

Chemiluminescence determination of sulfite in sugar and sulfur dioxide in air using Tris(2,2'-bipyridyl)ruthenium(II)-permanganate system

A chemiluminescence (CL) detection for the determination of sulfite using the reaction of Ru(bipy)(3)(2+) (bipy=2,2'-bipyridyl) -SO(3)(2-)-KMnO(4) is described. The concentration of sulfite is proportional to the CL intensity from 5.0x10(-8) to 1.25x10(-4) mol l(-1). The limit of detection is 2.5x10(-8) mol l(-1) and the relative standard deviation is 4.9% for the 2x10(-5) mol l(-1) sulfite solution in six repeated measurements. This method has been successfully applied to the determination of sulfite in sugar and sulfur dioxide in air by using triethanolamine (TEA) as the absorbent material.     

Photoluminescent layered Y(III) and Tb(III) silicates doped with Ce(III)

The synthesis and structural characterization of new layered rare-earth silicates K(3)[M(1-a)Ce(a)Si(3)O(8)(OH)(2)], M = Y(3+), Tb(3+), a < 1 (AV-22 materials), have been reported. These materials combine the properties of layered silicates, such as intercalation chemistry, and photoluminescence and may find applications in new types of sensor devices. For mixed Tb/Ce-AV-22, evidence has been found for the energy transfer from the large Ce(3+) 4f( 1) --> 5d(1) broad band to the sharp Tb(3+) 4f (8) lines. This energy transfer allows the fine-tuning of the color emission in the blue-green region of the chromaticity diagram. Upon Ce(3+) excitation (342 nm), the radiance of Tb/Ce-AV-22 is approximately 2 times higher than that measured under direct Tb(3+) excitation, which reinforces the existence of effective room-temperature Ce(3+)-to-Tb(3+) energy transfer.