Enzyme-linked Immunosorbent Assay in Quality Control of Chinese Medicines： A Review / 中国实验方剂学杂志

In the quality control of Chinese medicine， the detection of active components and toxic and harmful components are two important links. Although conventional methods such as high performance liquid chromatography and liquid chromatography-mass spectrometry can accurately quantify the above substances， they have shortcomings such as complicated operation， high costs， inability of detection at any time， difficult detection of insoluble and macromolecular substances. Enzyme-linked immunosorbent assay （ELISA） can adsorb antigens or antibodies on the surface of solid carriers and realize qualitative or quantitative analysis of targets by using the specific reactions of antigens and antibodies. This method is praised for the simple operation， high sensitivity， strong specificity， simple requirements for experimental equipment， a wide application range， and low costs. In recent years， ELISA has been widely used in the quality control of Chinese medicine， especially in the content determination of mycotoxins represented by aflatoxin and the qualitative and quantitative analysis of active components. ELISA plays an increasingly important role with its unique advantages， providing new methods and ideas for the rapid quality examination of large quantities of Chinese medicines. This paper reviews the research progress in ELISA for the quality control of Chinese medicine in recent years and prospects its technical development and application prospects， aiming to provide reference and research ideas for further using this method to ensure the quality， safety， and controllability of Chinese medicine.

Research progress of pesticide residues in Chrysanthemum / 中国中药杂志

Chrysanthemum is widely used as a type of edible flower and also considered as the important materials of many beverages in China. Due to the occurrence of diseases and pests, and the lack of regulations for species, frequency, dose of pesticides in Chrysanthemum, pesticides have become one of the main pollutants in Chrysanthemum. The pesticide residues in Chrysanthemum were detected frequently and worth noting. This paper focused on the types of pesticides, pesticide residue detection techniques, and risk assessment methods for Chrysanthemums on the basis of relevant literatures. The pesticide residues of traditional Chinese medicine are mainly organochlorines, organophosphorus and pyrethroids, and the detection techniques include gas chromatography(GC), liquid chromatography(LC) or both combined with mass spectrometry(MS). With the increasing use of traditional Chinese medicine, Chrysanthemum is widely circulated in the market. Therefore, it is important to understand the current situation of pesticide residues in different varieties of Chrysanthemum, so as to provide theoretical reference for the control of quality and safety of Chrysanthemum and the formulation of the maximum residue limit.

Recent advances in surface-enhanced Raman scattering technique for pollutant detection in Chinese medicinal material / 中国中药杂志

Chinese medicinal material is the foundation of traditional Chinese medicine(TCM) industry. Its quality is not only closely related to the health of residents but also the key to the development of the TCM industry. Pesticide residues, heavy metals and mycotoxins are the major pollutants of Chinese medicinal materials. In recent years, quite a number of rapid detection methods for pollutants have been constructed. Among them, surface-enhanced Raman scattering(SERS), which has been widely used in food chemistry, environmental analysis, and other fields because of its speediness and non-destructiveness, shows its great potential in the pollutant detection in Chinese medicinal material. This paper firstly reviews the application of SERS for the detection of common pollutants in Chinese medicinal material. We then discussed the characteristics and advantages of SERS technique for pesticide detection, including the principle, SERS substrate design, specific recognition, etc. Finally, simultaneous detection of multiple pesticide residues in Chinese medicinal material was explored.

Pesticides `contamination of lactating mothers’ milk in the north-western Himalayan region of India

Aim: The objective of the study was to develop and characterize the properties of sago (sabudana) from cassava based reconstituted dry starch with addition of pre-gelatinized starch and wet starch as binders.Methodology: The dry starch was soaked for 12 hrs at 30 % concentration and then sago was prepared at 40% moisture content with addition of pre-gelatinized starch and wet starch as binders in different treatment combinations. Results: The sago developed from the combination of reconstituted dry starch (75%) and wet starch (25%) had an optimal commercial size (3.36 mm) and shape (sphericity value, 76 %). The swelling power (5.98%) was high in reconstituted dry starch sago and solubility (13.42 %) was high in wet starch sago without the addition of any binders. The increase in cooking time (10.37%) and decrease in cooking loss (1.73%) were observed for sago developed with pre-gelatinized starch as binder. The lowest oil absorption index (0.45 g g-1) was noticed for sago prepared with wet starch as a binder. The storage modulus was comparatively lower for sago paste prepared using wet starch and thus the sago gel behaved like a dilute solution with increase in storage modulus and phase angle. Interpretation: The physico-functional properties of the cassava -based reconstituted dry starch sago can be improved by adding wet starch as a binder due to less retrogradation rate. Further, the addition of pre-gelatinized starch as a binder with reconstituted cassava dry starch can reduce the cooking loss in sago.

Research progress of pesticide residues in traditional Chinese medicines / 中国中药杂志

The residue of the pesticides is closely related to the quality and safety of traditional Chinese medicines(TCMs) and has attracted widespread attention at home and abroad.This article analyzed the current status of pesticide residues in TCMs by summarizing the research results of recent years.At the same time,the methods for the detection of pesticide residues in TCMs were summarized,and the domestic and foreign pesticide residue limit standards for TCMs were compared,intending to provide reference and basis for the detection and control of pesticide residues in TCMs.

Determination of 106 Pesticide Residues in Citrus Grandis Exocarpium / 中国药学杂志

OBJECTIVE: To establish a method for determination of pesticide residues in Citrus Grandis Exocarpium by mass spectrometry. METHODS: After vortex extraction with acetonitrile, the samples were purified with prime-HLB SPE. GC-MS/MS analysis was performed on a DB17 MS(30 m×0.25 mm, 0.25 μm)capillary column with electron impact(EI) source. LC-MS/MS analysis was performed on a Phenomenex Kinetex C18(2.1 mm×100 mm, 2.6 μm) column with gradient elution using water(containing 5 mmol•L-1 ammonium formate and 0.1% formic acid) and 95% acetonitrile(containing 5 mmol•L-1 ammonium formate and 0.1% formic acid). Electrospray ionization(ESI) source was applied by positive ionization in multiple reaction monitoring(MRM) mode. RESULTS: The calibration curves of 106 pesticide residues showed good linearity with correlation coefficients above 0.990 9. The average recoveries for all target compounds fell in the range of 57.6%-134.4%, with RSDs below 15%. Seven kinds of prohibited pesticides and 25 strictly restricted and commonly used ones were detected in 20 batches of samples, which mainly belong to insecticide, acaricide and fungicide. CONCLUSION: The method is fast, accurate and highly sensitive for the screening and confirmation of pesticide residues in Citrus Grandis Exocarpium, which provides a basis for the control of pesticide residues in similar mattrix medicinal plants.

Research Progress of Retention Index Principle in Rapid Screening and Quantitative Analysis of Pesticide Residues in Chinese Herbal Medicines / 中国药学杂志

The pesticide residues in traditional Chinese herbal medicines have seriously affected its safety of quality and international reputation, and have been widely concerned by the public and regulatory authorities. With the increasing demand for high-quality green Chinese medicine products, the frequency of quantitative determination of pesticide residues in traditional Chinese medicine products by the regulatory authorities will also increase significantly. It is imperative to establish a series of quantitative methods for pesticide residue analysis that are fast, simple, high-throughput, and low-cost. This paper mainly summarized the research status of pesticide residues analysis in Chinese herbal medicines, summarized the difficulties encountered in the analysis of pesticide residues in Chinese herbal medicines, and introduced the advantages of the retention index principle applied to the analysis of pesticide residues in Chinese herbal medicines. This paper highlights the research progress of retention index principle combined with the Smart Database-Pesticides database applied to three exemplary examples, including: the quantitative determination of 12 pyrethroid pesticide compounds in Anisi Stellati Fructus, the quantitative determination of 74 pesticide compounds in Chuanxiong Rhizoma, and quantitative determination of 130 pesticide compounds in Panacis Quinquefolii Radix. The purpose of this paper is to make retention index principle more popular in the rapid analysis of pesticide residues in traditional Chinese herbal medicines.

Immunochromatographic Assay for Detection of Imidaclothiz Based on Upconversion Fluorescence Labeling / 分析化学

A simple,rapid and sensitive upconversion immunochromatographic assay(UICA) was developed to detect imidaclothiz using NaYF4:Yb,Er upconversion nanoparticles(UCNPs) labeled with anti-imidaclothiz monoclonal antibody. The amino-modified UCNPs were conjugated with anti-imidaclothiz monoclonal antibody to prepare the UICA strip,which could realize the quantitative detection of imidaclothiz using a fluorescence photometer with an external 980 nm laser source. The working conditions of the UICA were systematically optimized, and the sensitivity, specificity, precision and accuracy were assessed by the studies of cross-reactivity (CR), spiked recovery and validation with HPLC. Under the optimal conditions (pH 8. 0, 0.3 mol/L NaCl,2.5% methanol and 0.2% PEG2000), the UICA could be completed in 25 min for the detection of imidaclothiz. The half-maximal inhibition concentration (IC50), limit of detection (IC10) and linear range (IC10-IC90) were 97.37 ng/mL,26.30 ng/mL and 26.30-363.08 ng/mL, respectively. The UICA had no CR with the analogues of imidaclothiz except for imidacloprid. The average spiked recoveries were 71.8%-97.2% with the relative standard deviations of 0.7%-10.7% in the matrices of paddy water, soil,pear,peach,wheat,cucumber,tomato and rice. The detection results of UICA for the authentic paddy water and pear samples were consistent with that of high performance liquid chromatography (HPLC).

Analysis of Pesticide Residues in Wolfberry and Dietary Exposure Risk Assessment / 中国药学杂志

OBJECTIVE: To assess the levels of pesticide residues in Wolfberry and evaluate the intake exposure of pesticide residues. METHODS: A total of 332 kinds of pesticides in 40 samples collected from different areas were determined and dietary intake exposure risks were assessed. Risk assessment was conducted by using deterministic approach for the pesticides with detection rate over 20%. RESULTS: The analysis showed that 94% of the samples contained low levels of pesticide residues, and 85% of the samples contained five or more kinds of pesticide residues. Totally 31 pesticides were detected, most of which have low or moderate toxicity. However, carbofuran which is forbidden in Chinese herbs was detected. Risk assessment found that carbofuran had the highest acute risk and chronic risk, with risk probabilities of 89.523% and 2.000%, respectively. As the values were below 100%, it was indicated that the threat of this pesticide in Wolfberry to human health is acceptable. CONCLUSION: The maximum residue limit of carbofuran in Wolfberry should be established as soon as possible. In this study, deterministic model is used to assess the risk of pesticide residues in Chinese Wolfberry, with the aim to propose an appropriate assessment model for traditional Chinese medicine and provide data for maximum residue limit.

Investigation and Analysis of Pesticide Residues in Fructus Trichosanthis / 中国药学杂志

OBJECTIVE: To investigate the status of pesticide residues in Fructus Trichosanthis. METHODS: Seventy kinds of pesticide residues were detected by GC-MS-MS and 150 kinds of pesticide residues were detected by HPLC-MS-MS in 84 samples of Fructus Trichosanthis from leading producers of 11 provinces. RESULTS: The detection rate of pesticide residues in 84 Fructus Trichosanthis samples was 95.2%, with only 4 batch of samples without pesticide residues detection. Endosulfan sulfate, diphenlamine, fenvalerate, chlorantraniliprole, carbendazim, cyhalothrin, and bifenthrin had the highest detection rates, all above 10%. CONCLUSION: The detection rate of pesticide residues in Fructus Trichosanthis is high, but most of the detected pesticides have low contents, with few samples exceeding the limits.

Multi-Residue Analysis of Pesticides in Radix Ophiopogonis by GC-MS/MS / 中国药学杂志

OBJECTIVE: To establish a method for simultaneous determination of 56 kinds of pesticide residues in Radix Ophiopogonis by using gas chromatography tandem mass spectrometry (GC-MS /MS), and apply it to screening of 137 batches of samples. METHODS: The forbidden, restricted and frequently-used pesticides were selected as the detecting indexes. The samples were prepared by QuEChERS, and quantitative analysis was carried out by GC-MS /MS in multiple-reaction monitoring (MRM) mode. There were three supplemental levels for detection recoveries and RSD. RESULTS: All the 56 pesticides had good linearity in certain ranges with correlation coefficients(r) higher than 0.997 8. The recoveries of 96.4% pesticides ranged from 60% to 130% at three supplemental levels (1, 2 and 10 LODs), with the RSDs of 92.9% pesticides less than 15%. The LODs for most of the selected pesticides were below 0.01 mg•kg-1. Twelve pesticides were detected in 137 batches of samples. CONCLUSION: The detecting indexes are meaningful and the developed method is simple, rapid, sensitive and reliable for screening multiple pesticide residues in Radix Ophiopogonis. The test result has certain reference value for the cultivation and distribution supervision of Radix Ophiopogonis.

Construction of Nano Silver Modified Super Hydrophobic Interface for Detection of Trichlorfon Pesticides / 分析化学

Super hydrophobic interface modified with silver nanoparticles was fabricated for the detection of pesticide residues.By using a chemical reduction method,silver nanoparticles were deposited on the substrate surfaces with different microscopic pore structures.Two kinds of composite substrates,including regular stainless steel mesh and cellulose polyester film,were used.The pre-treatment of the substrate with fluoridated reagents was used to form a super hydrophobic interface,which made the target molecules on the surface concentrate effectively.The surface with the cellulose polyester substrate was used to detect Rhodamine 6G (R 6G) effectively with surface enhanced Raman scattering (SERS) technique.The results showed that the detection hmit was 10-16 mol/L.In addition,the surfaces based on the stainless steel mesh and cellulose polyester substrate were used to detect trichlorfon pesticide with detection limits of 1 × 10-15 mol/L and 1 × 10-16 mol/L,respectively.

Situation analysis and standard formulation of pesticide residues in traditional Chinese medicines / 中国中药杂志

Chinese Pharmacopoeia provides nine pesticide Maximum Residual Limits(MRLs) of traditional Chinese medicines(TCMs), The number of pesticides used in production are far more than those listed in pharmacopoeia. The lack of the standards make it's hard to reflect the real situation of pesticide residues in TCMs correctly. The paper is aimed to analyze the data of pesticide residues in TCMs from 7 089 items in 140 reports, and judging the exceedance rate of pesticides in TCMs using the MRLs of European pharmacopoeia，which is widely accepted in many countries. The results show that：①Pesticide residues in 18 kinds of TCMs are higher than MRLs，while in 137 kinds are below MRLs, such as Atractylodis Macrocephalae Rhizoma, Menthae Haplocalycis Herba and Fritillariae Thunbergii Bulbus. The average exceedance rate of all TCMs is 1.72%. The average exceedance rates of organochlorine, organophosphorus and pyrethroid are 2.26%, 1.51%, 0.37%，respectively. ②The average exceedance rate of pesticides is 2.00%, and the exceedance rate is more than 5%, accounting for 8.33%, the exceedance rate is between 1%-5%, accounting for 18.75%. the exceedance rate is between 0%-1%, accounting for 18.75%. The remaining 29 kinds of pesticides were not exceeded, accounting for 60.42%.Some reports like Greenpeace's organization exaggerated the pesticide residues in TCMs.But the pesticide residue question is still worthy of attention, so we proposed to amend the Chinese Pharmacopoeia pesticide residues standards, to increase the pesticide species of traditional Chinese medicine in production on the basis of retaining the existing types of pesticide residues, to strengthen the system research of pesticide residues in TCMs, providing a basis for making standard and promoting import and export trade in TCMs.

Advances on nanoparticles-tagged visual test strips for the rapid detection of pesticides / 中国中药杂志

The residue of the pesticides affects seriously the quality and safety of traditional Chinese medicine. Pesticide residue has caused ever-growing attention of people at home and abroad. Rapid detection techniques used for rapid screening of pesticide residues have expanded in a fast progress. As one of the fast development methods of rapid detection, visualization test strip based on nanoparticle has received much concern in recent years. This article focused on the classification of detection test strips and key factors on the fabrication of nanoparticle-based visualization test strips used in small molecule pesticides. Moreover, a wide application of nanoparticles-tagged test strips on pesticide residue was reviewed including single residue detection, multi residue detection, as well as quantitative analysis. Finally, the future application of visual test strip for detecting of pesticide residues in traditional Chinese medicine was forecasted, intending to provide the reference for rapid detection techniques on pesticide residues screening in herbal medicine industry.

A Research on the Limited Amount Index of the Pesticide Residue and Heavy Metal Content of Notoginseng Medicinal Materials and Slices Based on the Pollution-Free Quality / 世界科学技术-中医药现代化

This study analyzed the pesticide residue and heavy metal contents in Panaxnotoginseng (Burk.) F.H.Chen to provide the basis for the quality criterion of pollution-freemedicinal materials and slices of notoginseng.We randomly collected 100 samples of notoginseng from farmer's markets,producing areas of notoginseng and internet markets.We entrusted the third-party authoritative testing institutions to detect 203 items of the pesticide residues and 4 items of heavy metals.According to relative standards of Japan,Korea,the United States and the European Union,we analyzed and summarized the data in this study.We confirmed the 25 species of pesticides with high operating frequency and detection rate and the limited amount index of 4 heavy metals.In conclusion,these results enriched the limited amount index of the pesticide residues and heavy metal contents based on the previous notoginseng standard system serving as the quality criterion of pollution-free notoginseng,which was applicative and operable.

Discussion on present situation of study on pesticide residues in Chinese herbal medicines / 中国中药杂志

Pesticide residues in traditional Chinese medicine has attracted widespread attention at home and abroad. This paper analyzed the pollution present situation and existing problems of pesticide residue for Chinese herbal medicines, explicited the analytical methods of pesticide residues in Chinese herbal medicines. Meanwhile, the commonly used pesticide residue degradation and application in Chinese herbal medicines were discussed. Moreover, on the basis of analysis of pesticide residue standards, this paper proposed the necessity and urgency of the limit standard of pesticide residues in Chinese herbal medicines, and provided a scientific references for deepening research and developing safe, green medicines.

Determination of forbidden and restricted pesticides in flowers and fruits of traditional chinese medicines / 中国药学杂志

OBJECTIVE: To establish a method for simultaneous determination of 187 kinds of pesticides in flowers and fruits of traditional Chinese medicine (TCM) by using gas and liquid chromatography tandem mass spectrometry, taking medlar and honeysuckle as examples. METHODS: The forbidden, restrictted and commonly used pesticides were picked out as detecting indexes according to the principals of risk management. The factors affecting the extraction, purification, and detection were optimized, and the final condition was established as follows: the samples were extracted with acetonitrile, and cleaned-up by carb solid phase extraction column. The separation of target compounds were performed by capillary or liquid column, and quantitative analysis was carrid out by GC-MS/MS or LC-MS/MS with MRM model. Internal standard was used to improve the accuracy of this method. RESULTS: Honeysuckle flower and Wolfberry were used to evaluate the accuracy of this method. The calibration curves were linear in the range of 1-100 ng · mL-1 with correction coefficients of greater than 0.99. The recoveries of more than 88% pesticides were ranged from 70% to 120% at three spiked levels (5, 20 and 100 μg · kg-1). CONCLUSION: The detecting indexes in this method cover most forbidden and restricted pesticides, which is meaningful for the safety supervision of TCM. With the advantage of rapidness and accuracy, this method can be used for routine determination of multi-pesticides in flowers and fruits of TCM.

Analysis of Heavy Metals and Pesticide Residues in Codonopsis Radix / 中国药房

OBJECTIVE:To establish a method for the determination of heavy metals and pesticide residues in Codonopsis Ra-dix to evaluate the safety of Codonopsis Radix commercially available in Taiyuan city. METHODS:Gas chromatography was used to determine the residues of organochlorine pesticides in Codonopsis Radix. The column was DB-1701 fused silica capillary col-umn,detector was 63Ni-ECD electron capture detector,carrier gas was high-purity nitrogen,volume temperature was 210℃,detec-tor temperature was 300 ℃ and volume injection was 1 μl. ICP-MS method was conducted to determine the contents of Pb,Cd, Hg and As. High frequency transmitter power was 1 500 W,temperature of premix chamber was 2 ℃,flow rate of cooling gas was 15.0 L/min,flow rate of carrier was 0.8 L/min,peristaltic pump speed was 0.1 ml/s,compensation flow rate was 0.3 L/min and volume depth was 8 mm. RESULTS:The linear range of organochlorine pesticides was 4-100 μg/L(r≥0.995 0). RSDs of pre-cision,stability and reproducibility tests were not higher than 13.7%,recovery was 97.0%-104.0%(RSD≤1.9%,n=9). Linear re-gression equations of Pb,Cd,Hg and As were 0~0.025、0~0.025、0~0.005、0~0.025 μg/ml(r≥0.999 2),respectively. RSDs of precision,stability and reproducibility tests were not higher than 9.3%,average recoveries was 95.0%-106.7%(RSD≤3.8%,n=9). CONCLUSIONS:The method is simple,sensitive and accurate,and can be used for the determination of heavy metals and parts of pesticide residues in Codonopsis Radix. The contents of heavy metals and organochlorine pesticide residues in Codonopsis Radix are comformed to national limits.

Rapid determination of four categories of pesticide residues in toddaliae asiaticae (L.) lam. by carb/NH2-SPE-GC-MS / 中国药学杂志

OBJECTIVE: To establish a Carb/NH2-SPE-GC-MS method for rapid monitoring of 40 kinds of pesticides of four categories in Toddaliae asiaticae (L.) Lam. METHODS: The samples were pretreated with Carb/NH2 solid phase extraction (SPE) subpost, and a GC-MS method was used for the determination of the trace pesticide residues. RESULTS: In comparison with the pesticide residue pretreatment methods included in the Chinese Pharmacopoeia, the Carb/NH2-SPE-GC-MS method showed no significant differences (P>0.05) and was simpler and more feasible in handling a variety of pesticide residues in Toddaliae asiaticae (L.) Lam. Good linearity was obtained for the calibration curves for the 40 kinds of pesticides in the concentration range of 10 to 200 ng·mL-1 (r>0.998 2), the limits of detections (LODs) were around 2.5 ng·mL-1, and the precisions, stabilities and recoveries basically met the methodological requirements. CONCLUSION: Carb/NH2-SPE-GC-MS method established in this paper is simple, rapid, highly sensitive, and accurate for the qualitative and quantitative analysis of multi-component pesticide residues in Toddaliae asiaticae (L.) Lam.

Rapid Analysis of Three Kinds of Pesticide Residues by Non-contact Thermal Desorbing and Closing Low Temperature Plasma Ionization Mass Spectrometry / 分析化学

A new method was established for the direct, rapid and quantitative analysis of pesticide residues, dimethoate chlorothalonil and malathion by low temperature plasma ( LTP) ionization miniature ion trap mass spectrometer. The LTP ionization probe and sample inlet of ion trap mass spectrometry were enclosed in a metal cavity. With non-contact heating, the samples placed on the sample platform were desorbed into gaseous phase and ionized by LTP ionization probe. The results showed that closed ionization had an edge over the opened ionization. The quantitative analysis of 3 pesticides within the range of 0. 5-10 mg/L was realized by optimizing heating time and flow rate of air, and the relative standard deviations of signal intensity is less than 11%. LODs of pesticide, which were obtained within 5 s, were as low as several hundred pictograms. The results showed that the method could be used for the analysis of pesticide residue on green and organic fruits or vegetables.