Analyzing the difference between atomic fluorescence spectrometry and ICP-MS in the determination of arsenic in urine / 中国职业医学

@#Abstract: Objective （ ） To compare the measured results of arsenic in urine by atomic fluorescence spectrometry AFS and - （ - ）， Methods inductively coupled plasma mass spectroscopy ICP MS and analyze the reasons of the difference. The samples WS/T 474-2015 Determination of Arsenic in Urine by Hydride Generation Atomic Fluorescence were pretreated according to Spectrometry， （ ∶ ∶ ∶∶ ，V/V/V） and digested with mixed acid nitric acid sulfuric acid perchloric acid=3 1 1 and then determined by - - AFS and ICP MS. The samples were diluted with 0.50% nitric acid and determined by ICP MS. The samples included urine ， ， （ arsenic quality control samples inorganic arsenic supplemented samples and organic arsenic arsenic choline and arsenic ） - betaine supplemented samples. Standard curve method was used to compare the results of AFS method and ICP MS method. Results （ ） （ ） The results of quality control samples by AFS method digestion and ICP-MS method without digestion were ， - within the range of reference values but the values obtained by AFS method were lower than those obtained by ICP MS method. - - - ， The recovery of AFS and ICP MS was 97.79% 100.82% and 99.55% 99.98% respectively. In the middle and high ， - （ P ） concentration groups the measured values of inorganic arsenic by AFS were lower than that by ICP MS all <0.01 . The （ ） - recovery of arsenic betaine and arsenic choline by AFS method digestion was only 2.17% 2.63%. The values of arsenic betaine （ ） - （ and arsenic choline measured by AFS method digestion were lower than those measured by ICP MS method without ） - （ ）（ P ）Conclusion digestion and ICP MS method digestion all <0.01 . The result of urine arsenic measured by AFS method - ， was lower than that measured by ICP MS method which may be related to the mixed acid digestion of AFS method. Keywords: ； - ； ； ； ； ；

Chemical constituents from Clausena excavata and their inhibitory activities against proliferation of synoviocytes / 中国中药杂志

The chemical constituents from the stems and leaves of Clausena excavata were isolated and purified by column chromatography with silica gel, ODS, Sephadex LH-20 and RP-HPLC. The chemical structures of the isolated compounds were identified on the basis of physicochemical properties, spectroscopic analysis, as well as the comparisons with the data reported in literature. Nineteen compounds were isolated from the 90% ethanol extract of the stems and leaves of C. excavata, which were identified as methyl orsellinate(1), syringaresinol(2), lenisin A(3), scopoletin(4), osthenol(5), N-benzoyltyrarnine methyl ether(6), N-p-coumaroyltyramine(7), aurantiamide acetate(8), 1H-indole-3-carboxaldehyde(9), furostifoline(10), clausenalansine E(11), 3-formylcarbazole(12), clausine L(13), clausine E(14), methyl carbazole-3-carboxylate(15), glycosinin(16), murrayafoline A(17), clausine H(18) and 2,7-dihydroxy-3-formyl-1-(3'-methyl-2'-butenyl)carbazole(19). Among these isolated compounds, compounds 1-11 were isolated from C. excavata for the first time, and compounds 1, 2 and 10 were isolated from the genus Clausena for the first time. In addition, this study evaluated the anti-rheumatoid arthritis activities of compounds 1-19 by measuring their anti-proliferative effects on synoviocytes in vitro according to MTS method. Compounds 10-19 displayed remarkable anti-rheumatoid arthritis activities, which exhibited the inhibitory effects on the proliferation of MH7 A synovial fibroblast cells with the IC_(50) values ranging from(27.63±0.18) to(235.67±2.16) μmol·L~(-1).

Chemical constituents from stems and leaves of semi-mangrove plant, Barringtonia racemosa / 中草药

Objective: To study the chemical constituents of the stems and leaves of semi-mangrove plant, Barringtonia racemosa. Methods: The chemical constituents of B. racemosa were separated and purified by silica gel, ODS, Sephadex LH-20 gel column chromatographies and preparative HPLC. Their structures were identified by physicochemical properties, spectroscopic analysis, as well as comparisons with the data reported in literature. Results: A total of 17 compounds were isolated from the 90% ethanol extract of the stems and leaves of B. racemosa, which were identified as chrysin (1), ayanin (2), genkwanin (3), rhamnocitrin (4), tricin (5), dillenetin (6), 5,3'-dihydroxy-7,4'-dimethoxyflavone (7), 5,7,3',4'-tetramethoxyflavone (8), 5-hydroxy-6,7,8,3',4'- pentamethoxy flavone (9), petasitolone (10), sarmentol F (11), dehydrovomifoliol (12), blumenol A (13), 10-hydroxyaristolan-9-one (14), alphitolic acid (15), oleanolic lactone (16), and 11,12-dehydroursolic acid lactone (17). Conclusion: All compounds are isolated from the genus Barringtonia for the first time.

Chemical constituents from stems and leaves of Clausena emarginata / 中国中药杂志

The chemical constituents from the stems and leaves of Clausena emarginata were separated and purified by column chromatographies on silica gel,ODS,Sephadex LH-20,and PR-HPLC. The structures of the isolated compounds were identified on the basis of physicochemical properties and spectroscopic analysis,as well as comparisons with the data reported in the literature. Sixteen compounds were isolated from the 90% ethanol extract of the stems and leaves of C. emarginata,which were identified as siamenol( 1),murrastanine A( 2),3-formyl-1,6-dimethoxycarbazole( 3),3-methoxymethylcarbazole( 4),3-methylcarbazole( 5),murrayafoline A( 6),3-formylcarbazole( 7),3-formyl-1-hydroxycarbazole( 8),3-formyl-6-methoxycarbazole( 9),murrayanine( 10),murrayacine( 11),girinimbine( 12),nordentatin( 13),chalepin( 14),8-hydroxy-6-methoxy-3-pentylisocoumarin( 15) and ethyl orsellinate( 16). Compounds 1-4,14-16 were isolated from C. emarginata for the first time. Among them,compounds 1,2,15 and 16 were isolated from the genus Clausena for the first time. All isolated compounds were evaluated for their cytotoxic activities against five human cancer cell lines: HL-60,SMMC-7721,A-549,MCF-7 and SW480 in vitro. Compounds 12 and 14 showed significant inhibitory effects against various human cancer cell lines with IC_(50) values comparable to those of doxorubicin.

Hydrogen alleviates high-level low-dose irradiation-induced injury of male reproductive system in mice / 第二军医大学学报

Objective To explore the protective effects of molecular hydrogen on high-level low-dose irradiation-induced male reproductive system injury in mice and the underlying mechanism. Methods Cultured spermatogonia-derived cell line GC-1 spg was randomized into control group, hydrogen group, 4 Gy radiation group and 4 Gy radiation+hydrogen group. The apoptotic rate of the cells was detected by flow cytometry assay at 24 h after treatment in each group. Seventy-two male BALB/c mice were randomized into control group, hydrogen group, 0.25 Gy radiation group, 0.25 Gy radiation+ hydrogen group, 0.5 Gy radiation group and 0.5 Gy radiation+hydrogen group, with 12 mice in each group. The hydrogen treatment was conducted by hydrogen-rich water administration and high-concentration hydrogen gas inhalation. At 24 h after treatment, the testes were dissected and sectioned for H-E staining, and blood samples from the internal canthus vein were collected to determine the levels of gonadotropin-releasing hormone (GnRH), follicle-stimulating hormone (FSH), luteinizing hormone (LH), and testosterone using ELISA. At 4 weeks after radiation, the bilateral epididymides were isolated to prepare sperm suspensions, and the DNA damage of the spermatozoa was examined using the neutral single cell gel electrophoresis. Results The 24 h apoptosis rate of GC-1 spg cells was significantly decreased in the 4 Gy radiation+hydrogen group compared with the 4 Gy radiation group (t=7.186, P<0.01). Hydrogen obviously reverted the histological damage of the testes induced by 0.5 Gy irradiation, significantly inhibited 0.25 Gy and 0.5 Gy radiation-caused surge of FSH (t=3.195 8, P=0.019; t=10.723 4, P<0.05), and significantly ameliorated comet tailing and damage of the sperm DNA at 4 weeks after radiation (tail area t0.25 Gy=16.592 3, t0.5 Gy=15.891 5; tail DNA t0.25 Gy=11.296 5, t0.5 Gy=13.785 0; tail DNA% t0.25 Gy=26.834 0, t0.5 Gy=10.325 7; tail length t0.25 Gy=16.865 4, t0.5 Gy=15.441 2; tail moment t0.25 Gy=26.979 4, t0.5 Gy=13.174 2; Olive tail moment t0.25 Gy=24.752 4,t0.5 Gy=6.896 1; all P<0.05). Conclusion Molecular hydrogen protects male mouse reproductive system from high-level low-dose radiation through reducing spermatogonium apoptosis, adjusting hormone disturbance and ameliorating sperm DNA damage.

Determination of five anticoagulant rodenticides in whole blood by high-performance liquid chromatography / 中国职业医学

OBJECTIVE: To establish a method for simultaneous detection of 5 anticoagulant rodenticides including brodifacoum, bromadiolone, flocoumafen, warfarin and difenacoum in whole blood by high-performance liquid chromatogarphy. METHODS: The 0. 5 m L of blood sample was extracted by 2. 0 m L ethyl acetate,then separated by Diamonsil C18 column( 250. 0 mm × 4. 6 mm × 5. 0 μm) using acid-ammonium acetate( 20. 0 mmol / L,p H = 5. 5) /methyl alcohol( 2∶ 8,V / V) as a mobile phase and detected by diode-array detector under the ultraviolet spectrum of 310 nm through high-performance liquid chromatogarphy. RESULTS: The good linear range of the 5 anticoagulant rodenticides was0. 50-10. 00 mg / L,and the correlation coefficients were > 0. 999 00. The detection limits of brodifacoum,bromadiolone,flocoumafen,warfarin and difenacoum were 0. 08,0. 06,0. 09,0. 04 and 0. 10 mg / L and the lower limits of quantitation were 0. 79,0. 58,0. 92,0. 45 and 0. 96 mg / L,respectively. The recovery rate was 98. 40%-104. 00%. The within-run relative standard deviation( RSD) was 0. 61%-7. 84%,and the between-run RSD was 1. 10%-9. 62%. The samples can be stored for 14 days in the refrigerator at 4 ℃. CONCLUSION: The method has advantages of simple operation,good separating effect,high sensitivity,precision and accuracy,which is suitable for detection of whole blood samples in rodenticide poisoning patients.

Determination of 1-bromopropane in human urine by headspace gas chromatography-mass spectrometry / 中国职业医学

OBJECTIVE: To establish a detection method for 1-bromopropane in human urine by headspace gas chromatography-mass spectrometry( GC-MS). METHODS: A 4. 00 m L portion of the urine sample was placed in a 15. 00 m L headspace vial and 20. 00 μL of 1-bromobutane internal standard solution( 204. 200 mg / L mass concentration) was added.The bottle cap was immediately sealed. The sample was heated to 80 ℃ with an equilibrium time of 20 minutes in the headspace device. The vapor in the headspace vial was separated by GSBP-FFAP( 30. 00 m × 0. 25 mm × 0. 25 μm)capillary chromatography column and the ion was used to carry out quantitative determination of 1-bromopropane in human urine. RESULTS: The good linearity range of 1-bromopropan mass concentration was 0. 025-1. 012 mg / L, and the correlation coefficient was 0. 999 8. The detection limit was 7. 5 μg / L( urine sample volume,4. 00 m L) and the limit of quantitation was 25. 0 μg / L( urine sample volume,4. 00 m L). The relative standard deviation( RSD) of within-run precision was 2. 61%-4. 08%,and the RSD of between-run precision was 2. 79%-6. 25%. The average recovery rate was99. 34%-105. 94%. CONCLUSION: The method of determining 1-bromopropane in human urine by headspace GC-MS has the features of high sensitivity,good linear relationship,low interference,good precision and easy operation,which is suitable for detecting 1-bromopropane mass concentration in human urine.

Detection of tin in human urine by atomic fluorescence spectrophotometry / 中国职业医学

OBJECTIVE: To establish a method for determination of urinary tin by atomic fluorescence spectrophotometry.METHODS: The graphite digestion instrument was used to digest 2. 50 m L urinary sample with 1. 50 m L concentrated nitric acid,hydrochloric acid( volume fraction 4. 00%) was added to a total constant volume of 10. 00 m L. After 2. 50 m L of thiocarbamide-ascorbic acid( mass concentration 100 g / L) was added,hydrochloric acid( volume fraction 4. 00%) was added to a total constant volume of 25. 00 m L( equivalent to urinary sample was diluted 10 times),1. 00 m L of the sample was collected and detected by atomic fluorescence spectrophotometry. RESULTS: The good linear relationship was shown in the range of 4. 00-200. 00 μg / L with a correlation coefficient of 0. 999 5. The limit of detection was 0. 20 μg / L. The recovery rates ranged from 100. 20% to 100. 84%. The within-run relative standard deviation( RSD) and between-run RSD were 0. 11%-2. 01% and 1. 37%-5. 58%,respectively. The samples can be stored for 7 days under the temperature of4 ℃. CONCLUSION: This method has the advantages of high sensitivity,precision and convenient operation,which is suitable for the daily determination of urinary tin in human.