This study aims to establish a method for the determination of As B,As C,DMA,As( Ⅲ),MMA and As( Ⅴ) by using HPLC-ICP-MS. A Dioncx Ion PacTMAS7( 4 mm×250 mm) column was used for the HPLC-ICP-MS method. The mobile phase was 100 mmol·L-1 ammonium carbonate-1. 5 mmol·L-1 ammonium dibasic phosphate( gradient elution) at a flow rate of 1 m L·min-1. The injection volume was 10 μL. The linear relationships of As B,As C,DMA,As( Ⅲ),MMA,As( Ⅴ) were good with the concentration of10-500 μg·L-1. The average recovery rates( n = 6) were 105. 7%,100. 5%,102. 9%,105. 7%,100. 2%,92. 69%. The RSD were0. 50%,2. 4%,0. 93%,1. 3%,0. 89%,1. 5%. The precision and repeatability of this method were good. In this study,six forms of arsenic were separated effectively by this method. With methodological validation and sample determination,this method can be used to determine the morphological valence of arsenic in content determination.
Arsenic/analysis* ; Arsenicals/analysis* ; Chromatography, High Pressure Liquid ; Mass Spectrometry

As arsenic widely exists in nature and has been used in the pharmaceutical preparations, the traditional Chinese medicine(TCM) with arsenic include realgar(As_2S_2 or As_4S_4), orpiment(As_2S_3), and white arsenic(As_2O_3). Among the above representative medicine, the TCM compound formulas with realgar are utilized extensively. Just in Chinese Pharmacopoeia(2020 edition), there are 37 Chinese patent medicines including realgar. The traditional element analysis focuses on the detection of the total amount of elements, which neglects the study on the speciation and valence of elements. The activity, toxicity, bioavailability, and metabolic pathways of arsenic in vivo are closely related to the existence of its form, and different forms of arsenic have different effects on organisms. Therefore, the study on the speciation and valence of arsenic is of great importance for arsenic-containing TCMs and their compound formulas. This paper reviewed four aspects of the speciation and valence of arsenic, including property, absorption and metabolism, toxicity, and analytical assay.
Arsenic/analysis* ; Arsenicals/analysis* ; Sulfides ; Arsenic Trioxide ; Medicine, Chinese Traditional ; Drugs, Chinese Herbal/analysis* ; Biological Products

OBJECTIVETo develop a method for determining arsenobetaine (AsB), arsenite (AsIII), arsenate (AsV), Monomethylarsonic acid (MMA) and Dimethylarsenic acid (DMA) with liquid chromatography (LC), on-line UV-decomposition (UV), hydride generation (HG) and atomic fluorescence spectrometry (AFS) in animal origin seafood samples.

METHODSArsenic compounds were extracted in an ultrasonic bath with methanol-water (9:1) solvent from the animal origin seafood samples. The extracts were evaporated with N2 and dissolved in water. The solvent was extracted by hexane to remove lipids. And then, the aqueous solution was diluted to 10 ml. The extracts were filtered before analysis by LC-AFS. The mobile phase consisted of 0.5 mmol/L NH4H2PO4 (pH 9.0) and 20 mmol/L NH4H2PO4 (pH 6.0). Arsenic species were separated with an anion exchange column Hamilton PRPX-100 and gradient elution, detected by LC-UV-HG-AFS.

RESULTSThe established separation condition could achieve a better separation for five arsenic species. Detection Limits (LOD) were ranged from 0.0025 to 0.0032 mg/L, AsB was the predominant arsenic species in the animal origin seafood samples. AsIII and DMA were detected in certain shellfish samples at trace level. The accuracy of total arsenic measurement was tested by the analysis of NBS 1566 (Oyster Tissue). The accuracy of arsenic species measurement was tested by the analysis of BCR 627 (Tuna Fish). The data were tallied with the certified value.

CONCLUSIONArsenic species were specifically detected by LC-UV-HG-AFS in the animal origin seafood samples.

Animals ; Arsenic ; analysis ; Arsenicals ; analysis ; Chromatography, High Pressure Liquid ; methods ; Food Inspection ; methods ; Seafood ; analysis ; Spectrometry, Fluorescence ; methods

Arsenic ; urine ; Arsenicals ; analysis ; Environmental Monitoring ; methods ; Humans ; Sensitivity and Specificity ; Spectrometry, Fluorescence ; methods

OBJECTIVETo evaluate the association between metabolism of arsenic and DNA oxidative damage in workers in a arsenic mill.

METHODSUrinary organic arsenic and 8-hydroxydeoxyguanine were detected in 37 workers highly exposed to arsenic and 16 administrative and logistic staff with mild exposure in a arsenic mill in Yunnan province, and also 28 local people who did not have the exposure in the near past time. The correlation between metabolism of arsenic and DNA oxidative damage was evaluated.

RESULTSThe urinary organic arsenic concentration was respectively (0.48 +/- 0.37) mg/L and (0.08 +/- 0.05) mg/L for men with high and low exposure, and was respectively 0.11 mg/L and (0.30 +/- 0.24) mg/ L for women with high and low exposure, while it was lower than 0.02 mg/L in the controls. Urinary 8-hydroxydeoxyguanine concentration was (18.07 +/- 11.68) micromol/mol creatinine, (11.79 +/- 8.25) micromol/mol creatinine, (10.07 +/- 3.04) micromol/mol creatinine for the males with high and low exposure and of controls, respectively, (P < 0.05), and it was 84.35 micromol/mol creatinine, (21.27 +/- 5.89) micromol/mol creatinine, (14.43 +/- 2.58) micromol/mol creatinine for females with high and low exposure and of controls, respectively. The female workers exposed to arsenic had higher urinary 8-hydroxydeoxyguanine levels than males did (P < 0.05). The increased tendencies of urinary 8-hydroxydeoxyguanine levels with the organic arsenic concentration were found in workers (r(s) = 0.279, P = 0.019).

CONCLUSIONOccupational individuals exposed to arsenic have obvious DNA oxidative damage, which is more severe in females. The difference of metabolism of arsenic may play a key role.

Adult ; Arsenicals ; urine ; China ; Female ; Guanine ; analogs & derivatives ; urine ; Humans ; Male ; Middle Aged ; Occupational Exposure ; analysis

Sepiae Endoconcha is a common marine animal medicine,which generally contains high concentration of arsenic( As).The Chinese Pharmacopoeia( 2010 edition,part I) stipulated that the total As content of Sepiae Endoconcha should not exceed 2 mg·kg~(-1),while this limit was revised to 10 mg·kg~(-1) in the 2015 edition. So far,there is no research on the speciation of As in Sepiae Endoconcha,which made it hard to accurately evaluate its security risk. In this study,32 batches of Sepiae Endoconcha from different sources were collected. The safety risk assessment was carried out by determining the total As content and As speciation,inorganic As[As( Ⅲ),As( Ⅴ) ]and organic As( MMA,DMA,As C,As B) by HPLC-ICP-MS,and then the limit standard was discussed. The results showed that As B was the main form of As in Sepiae Endoconcha,followed by DMA and As( Ⅴ) ． Of the 32 batches of Sepiae Endoconcha,9 batches( accounting for 28%) were detected possessing i As. The maximum concentration of As( Ⅲ) was 103. 3 μg·kg~(-1),and the maximum concentration of As( Ⅴ) was 222. 4 μg·kg~(-1). According to the limit of i As in food,18. 75% of the samples exceeded the standard. The results indicate that there is no simple positive correlation between total As and As morphology in Sepiae Endoconcha. Besides,there is a risk in the total As limit,especially after the relaxation of the total As limit. The problem of high i As content caused by pollution and other factors is difficult to regulate. Since the toxicity of inorganic As is much higher than that of organic As,it is of great practical significance to establish inorganic As form limits in Sepiae Endoconcha.
Animals ; Arsenic/analysis* ; Arsenicals/analysis* ; Chromatography, High Pressure Liquid ; Drug Contamination ; Environmental Pollution ; Mass Spectrometry ; Medicine, Chinese Traditional ; Sepia/chemistry*

OBJECTIVE: To explore the effect of realgar on the gene expression profiles of multiple myeloma cell line RPMI 8226 by apply cDNA microarray. METHODS: The gene expression of RPMI 8226 cells before and after 48 hours of realgar treatment was determined with a cDNA microarray representing 4096 human genes. RESULTS: At the mRNA level, 164 genes were differentially altered; 53 genes were up-regulated; and 111 genes were down-regulated. CONCLUSION The realgar treatment to RPMI 8226 cell line may induce a number of gene changes. Many genes may be involved in the pathogenesis of multiple myeloma. BTG1, ALK1, and TXNIP genes may play an important role in the apoptosis and differentiation of RPMI 8226 cells.
Arsenicals ; pharmacology ; Gene Expression Profiling ; Humans ; Multiple Myeloma ; pathology ; Oligonucleotide Array Sequence Analysis ; Sulfides ; pharmacology ; Tumor Cells, Cultured

Adult ; Air Pollutants, Occupational ; adverse effects ; analysis ; Arsenicals ; adverse effects ; analysis ; Female ; Humans ; Male ; Metallurgy ; Middle Aged ; Occupational Exposure ; adverse effects ; Young Adult

PURPOSE: An arsenical compound, As2O3, has been reported to be effective for treating acute leukemia and inducing apoptosis in many different tumor cells. In this study, the ability of As4O6 to suppress cell growth and induce gene expression patterns was tested using a cDNA microarray in HPV16 immortalized cervical carcinoma cells, SiHa cells, along with As2O3. MATERIALS AND METHODS: A novel arsenical compound, As4O6, was designed and its ability to induce cell growth inhibition as well as gene expression profiles along with As2O3 in HPV16 infected SiHa cervical cancer cells was compared. Both As2O3 and As4O6 induced apoptosis in SiHa cells, as determined by DNA ladder formation. To further compare the gene expression profiles between these two drugs, a 384 cDNA microarray system was employed. Also, the gene expression profiles were classified into the Gene Ontology (GO) to investigate apoptosis-related cellular processes. RESULTS: As4O6 was more effective i suppressing the growth of SiHa cells in vitro compared to As2O3. In the case of treatment with As2O3, 41 genes were up- or down- regulated at least 2 fold compared to non-treatment. However, 65 genes were up- or down-regulated by As4O6 treatment. In particular, 27 genes were commonly regulated by both arsenic compounds. Also, the GO analysis indicated that down-regulation of cell-regulatory functions, such as cell cycle, protein kinase activity and DNA repair, induced anti-tumor effect. CONCLUSION: These data support that As4O6 could be more effective than As2O3 in inhibiting the growth of HPV16 infected cervical cancer cells. This appears to be mediated through a unique, but overlapping regulatory mechanism(s), suggesting that the regulated genes and cellular processes could be further used as a new potential drug approach for treating cervical cancer in clinical settings.
Apoptosis ; Arsenicals ; Cell Cycle ; DNA ; DNA Repair ; Down-Regulation ; Gene Expression ; Gene Ontology ; Leukemia ; Oligonucleotide Array Sequence Analysis ; Protein Kinases ; Transcriptome ; Uterine Cervical Neoplasms*

OBJECTIVETo explore arsenic accumulation and toxicity mechanism following long-term use of realgar and provide scientific basis for safety use of realgar in clinic.

METHODThe realgar which was used in the study contains 90% insoluble asenic sulfide (As2S2) and 1.696 mg x kg(-1) soluble arsenic. Two separate experiments were performed: 1) Twenty-eight fasting SD rats were orally given a single dose of realgar at the dose of 0.8 g x kg(-1) and the other four rats were given ultra-filtrated water served as control group. Blood, hearts, livers, kidneys, lungs and brains of four rats were taken out at 0.5, 1, 2, 4, 8, 16, 36 h respectively after treatment. Asenic quantity of each organ or blood sample was measured. 2) Forty SD rats were randomly divided into four groups: control group and realgar 0.02, 0.08, 0.16 g x kg(-1) groups, each group containing 5 females and 5 males. The rats were intra-gastrically treated with realgar once a day for successively 90 days, while the control group was given ultra-filtrated water. Asenic amount in blood, liver, kidney and brain of each rat was measured in fasting rats at 16 h after last dosing.

RESULTAsenic amount of blood, liver, kidney, heart, lung and brain increased after single dosing of realgar at dose of 0.16 g x kg(-1), with the order from high to low blood > kidney > lung > liver > heart > brain. Asenic amount was much higher in blood than that in other organs. The feature of asenic distribution in blood following realgar administration may be the basis for its use for leukemia Ninety-day oral treatment of realgar led to significant accumulation of asenic in blood, kidney, liver and brain. The highest asenic accumulation times was found in kidney followed by liver, which was assumed to be associated with nephrotoxicity and hepatotoxicity of realgar. The highest amount of asenic was observed in blood after 90 day's administration of realgar, and the amount of asenic in organs was in the order of blood > kidney > liver > brain.

CONCLUSIONAsenic can be absorbed and extensively distributed in various organs or tissesses after realgar administration in rats. Long-term use of realgar caused high asenic accumulation in various tissueses, including blood, kidney, liver, and brain. The nephrotoxicity and hepatotoxicity of realgar could be associated with the asenic accumulation in relative organs. Blood is the target of the most highest distribution and accamulation of asenic after realgar treatment, that could be associated with the efficacy of realgar on the treatment of leakemia.

Animals ; Arsenic ; analysis ; chemistry ; pharmacokinetics ; toxicity ; Arsenicals ; administration & dosage ; adverse effects ; chemistry ; Female ; Male ; Rats ; Rats, Sprague-Dawley ; Solubility ; Sulfides ; administration & dosage ; adverse effects ; chemistry ; Time Factors