Analysis of dissolved organic matters in Fu River of Baoding using three dimensional fluorescence excitation-emission matrix.

The fluorescence properties of dissolved organic matter (DOM) in Fu River in Baoding were investigated by three-dimensional fluorescence spectrometry. The type, distribution and origin of the DOM were estimated on basis of the position, number and intensity of fluorescence peaks in the spectra. Two types of fluorescence peaks were detected from Fu River. There are protein-like fluorescence peaks A with Ex/Em = 225-230/340 nm and soluble microbial metabolites peaks B with Ex/Em=275/340-350 nm. The protein-like fluorescence peaks and soluble microbial metabolites peaks were founded in different times and stations in Fu River. Certain correlation was observed between the fluorescence intensity of DOM and the water quality parameters of Fu River. Good correlation of different fluorescence peaks showed the same of source. The fluorescence intensity of the two types had a significant positive relationship with COD, TN, TP and NH3-N concentration, this phenomenon indicating that the fluorescence peaks can speculate the level of pollution of Fu River. These results provided a reference for the pollution control in Fu River.

Preparation of doxycycline-imprinted magnetic microspheres by inverse-emulsion suspension polymerization for magnetic dispersion extraction of tetracyclines from milk samples.

A magnetic dispersion extraction method was developed based on a molecularly imprinted magnetic microsphere (MIMM) for the selective clean-up and enrichment of tetracycline antibiotics from milk samples. The MIMMs were prepared by inverse-emulsion suspension polymerization, using doxycycline, trimethylolpropane trimethacrylate, acrylamide, methacrylic acid, and surface-modified Fe3 O4 as a template molecule, crosslinker, functional monomer, and magnetic component, respectively. Synthesis and extraction conditions were optimized for obtaining excellent affinity and high selectivity. The magnetism, covering amount, and selectivity of the magnetic microspheres were characterized by a vibrating sample magnetometer, thermogravimetric analysis, and a competitive recognition experiment. The MIMMs were applied to separate tetracycline antibiotics from milk samples by magnetic dispersion extraction, and an enrichment factor of 9.28 and a good sample clean-up were obtained. The average recoveries of four tetracycline antibiotics were obtained in the range of 74.5-93.8% with a precision of 1.2-5.2%. The LODs and LOQs of the proposed method were in the range of 7.4-19.4 and 24.7-64.7 µg/kg, respectively. The results indicated that magnetic dispersion extraction using MIMMs is a powerful tool for food-sample pretreatment with high selectivity and a simplified procedure.

[Identification of geographical origins of rice with pattern recognition technique by near infrared spectroscopy].

A rapid method was developed for discrimination of the geographical origins of rice with pattern recognition technique by near infrared spectrocopy (NIRS). A total of 119 geography signs product Xiangshui rice samples and 90 rice (Non-Xiangshui rice) samples produced from other places were analyzed by NIRS. After first derivative and smooth processing, principal component analysis (PCA) was used to reduce the dimensionality of the spectral data. Through the loading graph of the first three principal components, characteristic wave band (7 700-6 700, 5 700-4 300 cm(-1)) with max-relativity was determined. In whole wave, using agglomerative hierarchical cluster analysis and Fisher's linear discriminant, the discrimination of Xiangshui rice and Non-Xiangshui rice was all 100%. The correct rate of specific geographical origins of Non-Xiangshui rice was 91.9% by cluster analysis and 96.7% by discriminant analysis. For analysis in the characteristic wave bands, the correct rate of discriminant by cluster analysis was higher than the analysis result through the range of the whole band. Therefore, characteristic wave band has strong representativeness. The results indicate that it is feasible to discriminate the geographical origins of rice with pattern recognition technique by NIRS, and selecting characteristic wave band is one of the validated methods to improve the precision of the discrimination mode.

Degradation of naproxen by combination of Fenton reagent and ultrasound irradiation: optimization using response surface methodology.

A central composite factorial design methodology was employed to optimize the degradation of naproxen (NPX) by the combination of Fenton reagent and ultrasound (US) irradiation. In this study, the variables considered for the process optimization were the hydrogen peroxide, ferrous ion and NPX initial concentrations, while ultrasonic power amplitude was adjusted at 90% and initial pH was 3. An appropriate quadratic model was developed in order to plot the response surface and contour curves. Optimum dosage of Fenton reagent for NPX removal was found to be hydrogen peroxide concentration = 9.98 mmol L⁻¹, ferrous ion concentration = 4.83 mg L⁻¹ while NPX concentration was equal to 20 mg L⁻¹. A degradation efficiency of 100% was achieved within 10 min under US.

[Curve fitting based on genetic algorithms for quantitative resolution in overlapped fluorescence spectra].

The exponentially modified Gaussian (EMG) model-based genetic algorithm was used as a fitness function for fitting fluorescence spectrogram. The method was effective for solving the interference of fluorescent substance in the course of the multi-component quantitative analysis. As an example, the interference of endogenous fluorophores in different urines with the fluorescence of gatifloxacin (GFLX) was examined. A good eradicating efficacy was achieved by using the fitting fluorescence spectrogram. Under the optimized experimental conditions, the good linear relationship between the fluorescence intensity and GFLX concentration was obtained in the range of 0.06-3.5 microg x mL(-1) with a correlation coefficient of 0.9994. The detection limit and recovery were 0.02 microg x mL(-1) and 99.2%-109.4%, respectively, with the relative standard deviation from 1.3% to 2.7%. The proposed fitting fluorescence spectrometric method was rapid, simple and highly sensitive for the determination of GFLX in different human urine without preseparation. The recovery, selectivity, linearity, precision and accuracy of the method are convenient for routine assays and pharmacokinetic studies.

[Determination of 9 heavy metal elements in sediment by ICP-MS using microwave digestion for sample preparation].

A method for determining 9 heavy metal elements in soil and sediment was developed by using microwave digestion-ICP-MS. The mixture of HNO3-H2O2-HF was found to give the best digestion results for soil and sediment of samples. Under the optimized conditions, the samples were analyzed by ICP-MS with the triple internal standard elements Ge, In and Bi. The results showed that all their correlation coefficients were over 0.999. The national standard soil referenee material (ESS-1 GSBZ50011-88) was analyzed by the described method and the results were accorded with the reference values. The measurement precision range was from 0.48% to 5.73% in terms of relative standard deviation. The recoveries and the limits of detection were in the ranges of 98.0% to 100.7% and 0.011 to 0.328 microg x L(-1) respectively, and 11 sediment samples were determined by the proposed method. It was indicated that the method was reliable for determining heavy metal elements in soil and sediment samples.

Longitudinal changes in the hypothalamic-pituitary-adrenal axis and sympathetic nervous system are related to the prognosis of stroke.

Background and purpose: This study sought to improve methods to identify biomarkers in the neuroendocrine system related to stroke progression to improve the accuracy of traditional tools for evaluating stroke prognosis. Methods: Seventy-four stroke patients and 237 healthy controls were prospectively included. We measured urinary epinephrine (E), noradrenaline (NE), dopamine (DA) and cortisol (F) on days 1, 3, and 5 after stroke onset and plasma F, adrenocorticotropic hormone (ACTH), thyrotropin (TSH), prolactin (PRL), follicle-stimulating hormone (FSH), luteinizing hormone (LH) and growth hormone (GH). The correlation between these hormone levels and 90-day prognosis was analyzed, their value in assessing prognosis was compared with lesion volume and National Institutes of Health Stroke Scale (NIHSS) scores using receiver operating characteristic (ROC) curves, and their correlation with conventional clinical variables was assessed. Results: Levels of F, 24-h urinary free cortisol(UFC), E, NE, DA, and GH on days 1, 3, and 5 were significantly higher in stroke patients than in controls (P < 0.01), while ACTH and TSH decreased, gradually approaching normal within 5 days of onset. Levels of E, NE, F, and 24-h UFC were proportional to severity, and all gradually decreased within 5 days of onset in patients with a good prognosis and gradually increased or remained high in those with a poor prognosis. After adjustment for age, sex, NIHSS, or Glasgow Coma Scale (GCS) score, F > 13.6 µg/dL, ACTH > 22.02 pg/mL and NE > 123.5 µg/ 24 h were identified as risk factors for a poor prognosis 90 days after stroke (P < 0.05). The combination of F, ACTH, NE, white blood cell count (WBC), glucose (Glu), and hemoglobin (Hb) was significantly more accurate than lesion volume (AUC: 0.931 vs. 0.694 P = 0.019) and NIHSS score (AUC: 0.931 vs. 0.746 P = 0.034) in predicting poor prognosis of stroke 1 day after onset. Hormones and traditional clinical variables were correlated to varying degrees, with NE correlating most strongly with 24-h UFC (r = 0.54) and moderately positively with lesion volume (r = 0.40) and NIHSS score (r = 0.45). Conclusions: Stroke causes significant time-phased dynamic changes in the hypothalamic-pituitary-adrenal axis and sympathetic nervous system, and plasma F, ACTH, and urinary NE levels can be used to assess stroke severity and prognosis. Chinese clinical trial registry: Registration Number: ChiCTR1900024992. Registration Date: 2019/8/6.

[Studies on TCs-Fe(III) system separation/enrichment of trace tetracyclines antibiotic by combination ionic liquid [Hmim]PF6 solvent sublation with fluorescence spectroscopy determination].

It is the first time ionic liquid was applied to gas solvent sublation, which established a new method for separation/enrichment of tetracyclines (TCs) antibiotic based on ionic liquid gas solvent sublation. The optimizing experimental conditions were as follows: the mixture of ionic liquid 1-hexyl-3-methylimidazo lium hexafluorophosphats and ethyl acetate ([Hmim] PF6-EA, phi = 1/0.9) can be used as flotation solvent, Fe(III) ion was as trapping agent, pH of test solution was 7.6, the gas flow rate was 40 mL x min(-1), and the flotation time was 50 min. The complexes of TCs- Fe (III) were pre-concentrated in the [Hmim] PF6-EA layer and this was used to determine analytes by fluorescence method directly. The linear regression equation was F = 246.5c+4.32 (c: microg x 10 mL(-1)), and correlation coefficient was 0.999 1. Recoveries between 94.2% and 100.4% were achieved from surface water and sediment samples in ponder by using this method and the relative standard deviation of 5 microg x mL(-1) TCs for 5 parallel determinations was less than 3.2%. FTIR spectroscopy demonstrated that no chemical (bonding) interactions occurred between the ionic liquid and the complexes functional groups, and the ionic liquid was only solvent. The experimental result indicated that utilizing ionic liquid to float TCs in environmental sample is feasible.

Recognition mechanism of water-compatible molecularly imprinted solid-phase extraction and determination of nine quinolones in urine by high performance liquid chromatography.

Novel water-compatible molecularly imprinted polymers (MIPs) were synthesized in methanol-water systems with ofloxacin as templates and methacryclic acid as functional monomers. The MIPs were used as a special sorbent for the selective solid-phase extraction (SPE) of nine quinolones from urine samples, showing high affinity to the quinolones in aqueous environment. Its molecular recognition mechanisms were investigated by the molecular simulation and the experimental validation with UV and infrared spectrogram as well as (1)H NMR. Binding capability and chromatographic characteristic were also evaluated. By using the water-compatible MIPs as SPE sorbents, the nine quinolones can be selectively extracted and enriched, while all matrices interferences were eliminated simultaneously. Under the optimal conditions of SPE and high performance liquid chromatography (HPLC), the good linearity of the method was obtained in a range of 0.05-30microg/mL with the correlation coefficient of >0.999 and the relative standard division of 2.0-7.4%. The detection limits (s/n=3) were in a range of 0.036-0.10microg/mL. The proposed method was successfully applied for the selective extraction and separation of the studied quinolones in urine samples.

Decolorizing of azo dye Reactive red 24 aqueous solution using exfoliated graphite and H2O2 under ultrasound irradiation.

At its natural pH (6.95), the decolorization of Reactive red 24 in ultrasound, ultrasound/H2O2, exfoliated graphite, ultrasound/exfoliated graphite, exfoliated graphite/H2O2 and ultrasound/exfoliated graphite/H2O2 systems were compared. An enhancement was observed for the decolorization in ultrasound/exfoliated graphite/H2O2 system. The effect of solution pH, H2O2 and exfoliated graphite dosages, and temperature on the decolorization of Reactive red 24 was investigated. The sonochemical treatment in combination with exfoliated graphite/H2O2 showed a synergistic effect for the decolorization of Reactive red 24. The results indicated that under proper conditions, there was a possibility to remove Reactive red 24 very efficient from aqueous solution. The decolorization of other azo dyes (Reactive red 2, Methyl orange, Acid red 1, Acid red 73, Acid red 249, Acid orange 7, Acid blue 113, Acid brown 75, Acid green 20, Acid yellow 42, Acid mordant brown 33, Acid mordant yellow 10 and Direct green 1) was also investigated, at their natural pH.

Sonochemical decolorization of acid black 210 in the presence of exfoliated graphite.

The decolorization of acid black 210 by ultrasonic irradiation in the presence of exfoliated graphite was investigated. Low pH value and large exfoliation volume of exfoliated graphite favored the ultrasonic decolorization of acid black 210. The combination method of ultrasonic waves and exfoliated graphite achieved better results than either exfoliated graphite or ultrasound alone. Improved decolorization efficiency has been observed in the present system compared to the process using a combination of ultrasound and activated carbon. In the combination method of ultrasonic waves and exfoliated graphite, approximately 99.5% of acid black 210 was removed using 0.8 g/l exfoliated graphite at a pH of 1 within 120 min at 51 degrees C.

Determination of closantel residues in milk and animal tissues by HPLC with fluorescence detection and SPE with oasis MAX cartridges.

A liquid chromatographic method for the determination of closantel residues in milk and tissues is developed and validated. An acetonitrile-acetone solution (80:20, v/v) is used for the extraction of closantel residues from milk and animal tissues, and the extract is purified by solid-phase extraction with Oasis MAX cartridges and a mixture of formic acid-acetonitrile (5:95, v/v) as the elution solution. A C(18) bonded silica column is used for chromatographic separation. The mobile phase consists of acetonitrile-water (85:15, v/v) containing 0.05% triethylamine at pH 2.5, adjusted with phosphoric acid with the flow-rate set at 1.0 mL/min. Using the fluorescence emission of closantel at lambda(ex) = 335 nm and lambda(ex) = 510 nm, the calibration curve is linear, with a correlation coefficient of 0.9999 over the concentration range of 10-5000 microg/kg for the tissue sample and 10-5000 microg/L for the milk sample. The detection limit (s/n = 3) is 3 microg/kg for tissue sample and 3 microg/L for milk sample. The intra- and inter-day repeatabilities are between 3.35-7.66% and 4.04-8.67%, respectively. The proposed method enables the quantitative determination of closantel residues at levels as low as 10 microg/kg in animal tissue samples and 10 microg/L in milk samples.

[Investigation of enhancing effect for hydride generation-atomic fluorescence of transition metal elements].

A mechanism of hydride generation based on disassembly reaction of hydrogen-transferred interim state [M(BH4)m]* was developed by investigating the effect of reaction medium acidity on hydride generation. The effects of Co2+ and Ni2+, phenanthroline and 8-hydroxyquinoline on hydride generation-atomic fluorescence signals of Zn, Cd, Cu and Ni were studied, respectively, and their enhancing mechnism was discussed. The enhancing effect Co2+ and Ni2+ on the fluorescence signals of Zn and Cd was due to the increase in transmission efficiency of hydride of Zn and Cd. There was a synergic enhancing effect between phenanthroline or 8-hydroxyquinoline and Co2+ on the fluorescence signals of Zn and Cd, however no synergic enhancing effect between phenanthroline and 8-hydroxyquinoline on the fluorescence signals of Zn and Cd. The simulative action of cationic surfactant, anion surfactant and non-ionic surfactant surfactant to hydride generation was investigated. It is shown that both cationic surfactant and non-ionic surfactant have obvious enhancing effect on the fluorescence signals of analytes because of the decrease in surface tension of reaction solution. The release characteristics of hydride from the absorption solution containing surfactant was ulteriorly examined by using graphite furnace atomic absorption spectrometry, and the mechanism of enhancing effect of surfactant on hydride generation and transmission was proposed.

Determination of banned 10 azo-dyes in hot chili products by gel permeation chromatography-liquid chromatography-electrospray ionization-tandem mass spectrometry.

An accurate method based on the use of gel permeation chromatography (GPC)-liquid chromatography-tandem mass spectrometry interfaced with electrospray ionization (GPC-LC-ESI-MS/MS) was devised for the simultaneous determination of Sudan (I-IV), Sudan Orange G, Sudan Red B, Sudan Red G, Sudan Red 7B, Butter Yellow and Para Red in hot chili products. A GPC clean-up procedure was developed for simultaneous quantification of 10 dyes in hot chili and hot chili products avoiding some interference and permitting multiple injections without damaging the column. A HPLC was performed on an Inertsil C18 column using a multistep gradient elution with 0.1% formic acid and methanol as the mobile phase. Mass spectral acquisition was done in positive ion mode. Linearity of around three orders in the magnitude of concentration was generally obtained with the correlation coefficients (r2) of 0.9984-0.9997. Limit of detection (LOD) and limit of quantification (LOQ) for the investigated dyes were in the ranges of 0.1-1.8 and 0.4-5.0 microg/kg depending on matrices, respectively. The recoveries of the 10 synthetic dyes in five matrices ranged from 81.7 to 92.9%. The intra- and inter-day precision (RSDs) was between 2.9-7.8 and 3.9-8.1%, respectively. This method has been applied successfully for the determination of the studied 10 banned dyes in hot chili products.

Simultaneous determination of seven nitroimidazole residues in meat by using HPLC-UV detection with solid-phase extraction.

A method was developed for the determination of the seven nitroimidazoles including metronidazole (MNZ), ronidazole (RNZ), dimetridazole (DMZ), tinidazole (TNZ), ornidazole (ONZ), secnidazole (SNZ) and the common metabolite of RNZ and hydroxydimetridazole (DMOHZ) in poultry and pork muscles by high-performance liquid chromatography (HPLC) with ultraviolet detection (UV). After extraction with ethyl acetate and evaporation, the nitroimidazoles were redissolved in ethyl acetate and purified using strong cation exchange (SCX) solid-phase extraction (SPE) column. The HPLC separation was carried through on a C(18) bonded silica column with a deionized water-methanol-acetonitrile mobile phase using a gradient elution procedure. The limit of detection of all the seven nitroimidazoles was 0.2 microg/kg. The recoveries of the seven nitroimidazoles for chicken, pork and bacon samples spiked with 1-20 microg/kg were in the range of 71.4-99.5%. The linearity is satisfactory with a correlation coefficient of >0.998 at concentrations ranging from 0.7 to 60 microg/kg. The relative standard deviations of 10 measurements for spiked chicken, pork and bacon samples at the concentration of 1 and 20 microg/kg were in the range of 6.2-13.9% and 4.0-8.7%, respectively. The intra-day precision (n=5) for nitroimidazoles residues in chicken spiked at 20 microg/kg is 6.9%, and the inter-day precision for 5 days (n=25) is 11%. The method is capable of identifying nitroimidazole residues at > or =0.7 microg/kg levels and was applied in the determination of nitroimidazole residues in meat sample.

Effective separation and simultaneous determination of seven fluoroquinolones by capillary electrophoresis with diode-array detector.

A simple, rapid and accurate method has been developed for effective separation and simultaneous determination of lomefloxacin, gatifloxacin, enoxacin, ciprofloxacin, ofloxacin, enrofloxacin and pefloxacin residues in porcine tissue by capillary electrophoresis with diode-array detector. The separation conditions were investigated and optimized. The sample was extracted with acetonitrile, and a mixture consisted of 25 mM NaH(2)PO(4), 25 mM Na(2)B(4)O(7) and 25 mM H(3)BO(3) (pH 9.0) was used as a running buffer. A linear relationship between concentration and peak area for each compound was obtained in the concentration range of 0.5-100 mg/L with a correlation coefficient greater than 0.9994. For analysis of porcine tissue, the detection limits of lomefloxacin, gatifloxacin, enoxacin, ciprofloxacin, ofloxacin, enrofloxacin and pefloxacin were 0.013, 0.012, 0.023, 0.040, 0.037, 0.035 and 0.034 mg/kg, respectively. The recoveries are in the range of 72-93%. The intra-day precision is less than 5%, and the inter-day precision is less than 10%. The proposed method has high resolution, speed and the extremely small sample volume required. It can permit to confirm the presence of the studied seven fluoroquinolones in porcine tissue at the required maximum residue limit (MRL) level.

Decolorization of azo dye direct scarlet 4BS solution using exfoliated graphite under ultrasonic irradiation.

A combination of ultrasound and exfoliated graphite has been used to treat wastewater containing direct scarlet 4BS for colour removal and for the reduction of absorption at a wavelength of 242 nm. The results show that the ultrasound/exfoliated graphite process is effective in removing direct scarlet 4BS from aqueous solution. Furthermore, it can achieve better results than either exfoliated graphite or ultrasound alone.

Removal of disperse blue 2BLN from aqueous solution by combination of ultrasound and exfoliated graphite.

This paper reports an efficient and convenient removal of disperse blue 2BLN from aqueous solution by the combination of ultrasound and exfoliated graphite. The various affecting factors were studied. The removal ratio of disperse blue 2BLN is 96.9% for the initial concentration of 200 mg/L using 600 mg/L exfoliated graphite (exfoliation volume of 300 mL/g) at 45 degrees C within 120 min under ultrasound. The combination method was more effective than sonolysis or exfoliated graphite treatment individually.

[Determination of trace sodium ion in high purity water by graphite furnace atomic absorption spectrometry].

The present paper studied on the determination of trace Na+ in high purity water by graphite furnace atom absorption spectrometry. A method of directly on-line concentrating samples in graphite furnace, multiple charging, ashing, then determining once by directly charging into pools of graphite furnace, was set up. The goal of concentrating samples and avoiding contamination as well as raising sensitivity were finally achieved. To prevent the background of purity water and regent in experiment from covering the ion concentration of the sample, the authors prepared the high purity water and regent to meet the requirement of the experiment by electrodialysis in series with distillation and below-boiling-point quartz distillation at pure worktable. Satisfactory results of linearity and detection limit were obtained. The detection limit with this method was 0. 086 microg x L(-1) for Na+. The recovery was 101%-104%.

Characteristic of theophylline imprinted monolithic column and its application for determination of xanthine derivatives caffeine and theophylline in green tea.

Theophylline imprinted monolithic columns were designed and prepared for rapid separation of a homologous series of xanthine derivatives, caffeine, and theophylline by an in situ thermal-initiated copolymerization technique. Caffeine and theophylline were fully separated both under isocratic and gradient elutions on this kind of monolithic molecularly imprinted polymers (MIP) column. The broad peak showed in isocratic elution could be improved in gradient elution. Some chromatographic conditions such as mobile phase composition, flow rate, and the temperature on the retention times were investigated. Hydrogen bonding interaction and hydrophobic interaction played an important role in the retention and separation. The binding capacity was evaluated by static adsorption and Scatchard analysis, which showed that the dissociation constant (KD) and the maximum binding capacity (Qmax) were 1.50 mol/L, and 236 micromol/g for high affinity binding site, and 7.97 mol/L and 785 micromol/g for lower affinity binding site, respectively. Thermodynamic data (DeltaDeltaH and DeltaDeltaS) obtained by Van't Hoff plots revealed an enthalpy-controlled separation. The morphological characteristics of monolithic MIP were investigated by scanning electron microscope, which showed that both mesopores and macropores were formed in the monolith. The present monolithic MIP column was successfully applied for the quantitative determination of caffeine and theophylline in different kinds of green tea.