Volatile Compounds Fingerprints for White Duck down and White Goose down Determined by Gas Chromatography-Ion Mobility Spectrometry

This work first describes a simple approach for the untargeted profiling of volatile compounds for distinguishing between white duck down (WDD) and white goose down (WGD) based on resolution-optimized GC-IMS combined with optimized chemometric techniques, namely PCA. The detection method for down samples was established by using GC-IMS. Meanwhile, the reason of unpleasant odors caused by WDD was explained on the basis of the characteristic volatile compounds identification. GC-IMS fingerprinting can be considered a revolutionary approach for a truly fully automatable, cost-efficient, and in particular highly sensitive method. A total of 22 compounds were successfully separated and identified through GC-IMS method, and the significant differences in volatile compounds were observed in three parts of WDD and WGD samples. The most characteristic volatile compounds of WGD belong to aldehydes, whereas carboxylic acids from WDD were detected generated by autoxidation reaction. Meanwhile, the main reason of unpleasant odor generation was possibly attributed to the high concentration of volatile carboxylic acids of WDD. Therefore, the constructed model presents a simple and efficient method of analysis and serves as a basis for down processing and quality control.

A novel protein refolding method integrating ion exchange chromatography with artificial molecular chaperone

Artificial molecular chaperone （AMC） and ion exchange chromatography （IEC） were integrated, thus a new refolding method, artificial molecular chaperone-ion exchange chromatography （AMC-IEC） was developed. Compared with AMC and IEC, the activity recovery of lysozyme obtained by AMC-IEC was much higher in the investigated range of initial protein concentrations, and the results show that AMC-IEC is very efficient for protein refolding at high concentrations. When the initial concentration of lysozyme is 180 mg/mL, its activity recovery obtained by AMC-IEC is still as high as 76.6%, while the activity recoveries obtained by AMC and IEC are 45.6% and 42.4%, respectively.

Application of ion chromatography to the determination of water-soluble inorganic and organic ions in atmospheric aerosols

A simple, sensitive and convenient ion chromatography(IC) method was established for the simultaneous determination of twelve water-soluble inorganic anions(F -, Cl -, NO - 2, NO - 3, SO 2- 3, SO 2- 4, PO 3- 4), and fifteen water-soluble organic ions(formate, acetate, MSA, oxalate, malonate, succinate, phthalates, etc.) in atmospheric aerosols. The linear concentrations ranged from 0.005 μg/m 3 to 500 μg/m 3(r = 0.999—0.9999). The relative standard deviation(RSD) were 0.43%—2.00% and the detection limits were from 2.7 ng/m 3 to 88 ng/m 3. The proposed method was successfully applied to the simultaneous determination of those inorganic ions and organic ions in PM 2.5 of Beijing.

Liquid chromatography coupled with time-of-flight and ion trap mass spectrometry for qualitative analysis of herbal medicines

With the expansion of herbal medicine （HM） market, the issue on how to apply up-to- date analytical tools on qualitative analysis of HMs to assure their quality, safety and efficacy has been arousing great attention. Due to its inherent characteristics of accurate mass measurements and multiple stages analysis, the integrated strategy of liquid chromatography （LC） coupled with time-of-flight mass spectrometry （TOF-MS） and ion trap mass spectrometry （IT-MS） is well-suited to be performed as qualitative analysis tool in this field. The purpose of this review is to provide an overview on the potential of this integrated strategy, including the review of general features of LC-IT-MS and LC-TOF-MS, the advantages of their combination, the common procedures for structure elucidation, the potential of LC-hybrid-IT-TOF/MS and also the summary and discussion of the applications of the integrated strategy for HM qualitative analysis （2006-2011）. The advantages and future developments of LC coupled with IT and TOF-MS are highlighted.

Simultaneous determination of fluorine and iodine in urine by ion chromatography with electrochemical pretreatment

A new method for the simultaneous determination of fluorine and iodine in urine by ion chromatography （IC） with electrochemical pretreatment has been developed. The pretreatment was performed in a novel electrochemical oxidationneutralization device （EOND）, in which iodide of the sample was oxidized to iodate and the alkaline digestion sample solution was neutralized. Under the optimized conditions, the limits of detection （LOD, S/N = 3） were 2.5 μg/L for fluoride and 20 μg/L for iodate, respectively. The recoveries were in the range of 93-102% for fluoride and 86-98% for iodate.

Offline two-dimensional liquid chromatography coupled with ion mobility-quadrupole time-of-flight mass spectrometry enabling fourdimensional separation and characterization of the multicomponents from white ginseng and red ginseng

Inherent complexity of plant metabolites necessitates the use of multi-dimensional information to accomplish comprehensive profiling and confirmative identification.A dimension-enhanced strategy,by offline two-dimensional liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(2 D-LC/IM-QTOF-MS)enabling four-dimensional separations(2 D-LC,IM,and MS),is proposed.In combination with in-house database-driven automated peak annotation,this strategy was utilized to characterize ginsenosides simultaneously from white ginseng(WG)and red ginseng(RG).An offline 2 DLC system configuring an Xbridge Amide column and an HSS T3 column showed orthogonality 0.76 in the resolution of ginsenosides.Ginsenoside analysis was performed by data-independent high-definition MSE(HDMSE)in the negative ESI mode on a Vion?IMS-QTOF hybrid high-resolution mass spectrometer,which could better resolve ginsenosides than MSEand directly give the CCS information.An in-house ginsenoside database recording 504 known ginsenosides and 58 reference compounds,was established to assist the identification of ginsenosides.Streamlined workflows,by applying UNIFI?to automatedly annotate the HDMSEdata,were proposed.We could separate and characterize 323 ginsenosides(including 286 from WG and 306 from RG),and 125 thereof may have not been isolated from the Panax genus.The established 2 D-LC/IM-QTOF-HDMSEapproach could also act as a magnifier to probe differentiated components between WG and RG.Compared with conventional approaches,this dimensionenhanced strategy could better resolve coeluting herbal components and more efficiently,more reliably identify the multicomponents,which,we believe,offers more possibilities for the systematic exposure and confirmative identification of plant metabolites.

Determination of sulfur anions by ion chromatography-postcolumn derivation and UV detection

A novel method for determination of formaldehyde sulfoxylate, sulfite, thiocyanate, and thiosulfate in foodstuffs by ion chromatography separation with postcolumn derivation and UV detection has been developed. All species are separated at Dionex IonPac AG22A and AS22A with mobile phase of a mixture of 4.5 mmol/L sodium carbonate and 0.8 mmol/L sodium bicarbonate at a flow-rate of 1.0 mL/min. The postcolunm derivation solution was 0.24% iodine in 0.2% phosphate acid and the detection wavelength was set at 288 nm. The detection limits （LOD, signal-to-noise ratio of 3） of formaldehyde sulfoxylate, sulfite, thiocyanate, and thiosulfate were 0.004, 0.006, 0.006, and 0.007 mg/L, respectively. Within-day relative standard deviations （RSD, n = 10） of formaldehyde sulfoxylate, sulflte, thiocyanate, and thiosulfate were 3.24%, 3.76%, 2.68%, and 2.07%, respectively. The recoveries of the four anions were in the range of 67.2-116.5%.

Determination of haloacetic acids in hospital effuent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction （SPE） method was developed for the analysis of low concentration haloacetic acids （HAAs）, a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 ml/min, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples＇ turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μg/L and 1.30 μg/L, respectively, and the other three acids are ranging from 0.48 to 0.82μg/L under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.

Detection of Cyanide in Pollution-free Livestock Product Breeding Water by Ion Chromatography

In order to verify the accuracy of ion chromatography for cyanide detection,optimization conditions were studied,and comparison was made for the detection results of cyanide between titration and isonicotinic acid pyrazolone spectrophotometry. The results showed that ion chromatography has good linearity and reproducibility,with the recovery rate of 95%-105% and the limit of detection of 0. 001 mg/L. This method is simple,rapid,safe,selective,and suitable for the determination of cyanide in pollution-free livestock product breeding water.

Arsenic Speciation Analysis by Ion Chromatography - A Critical Review of Principles and Applications

Multiple acute and chronic toxicity of arsenic species and its mobilisation from geological deposits into ground and drinking water resources is one of the greatest threats to human health. Arsenic speciation analy-sis, mostly done by liquid chromatography, is a challenging task which requires an intense high quality work with respect to extraction, preservation, separation, detection and validation. A growing number of As-spe-cies and low regulatory limits (10 μg/L) may require more than one speciation method preferably performed by species specific procedures and detectors. Beside As-fractionation for special application there are many selective speciation methods based on high performance separation techniques like capillary electrophoreses, gas and liquid chromatography. Both, fractionation and speciation methods are reviewed. However, the focus is on scopes and limits of ion chromatographic separations, the most frequently used methods. Based on IC-principles the methods applied are critically discussed and recommendations given which should result in more robust and reliable As-speciation.

Separation Behavior of U(VI) and Th(IV) on a Mixed Ion Exchange Column Using 2,6-Pyridine Dicarboxylic Acid as a Complexing Agent and Determination of Trace Level Thorium in Uranium Matrix Employing High Performance Ion Chromatography

Retention behavior of U(VI) and Th(IV) as their 2, 6-pyridine dicarboxylic acid (PDCA) complexes on reversed phase and ion exchange (cation, anion and mixed ion exchange) columns was studied and based on the results, a simple ion chromatography method for the determination of trace level thorium in uranium oxide using 0.075mM 2, 6-pyridine dicarboxylic acid (PDCA) and 1M KNO3 in 1.2M HNO3 as eluent (flow rate 1 mL/min)was proposed. The advantage of the developed method is that the separation of uranium matrix is not required prior to the ion chromatographic determination of trace Th. Separation was carried out on a mixed ion exchange stationary phase and a 10?4 M arsenazo (III) solution was used as post column reagent for detecting the separated metal ions. The separation of Th from uranium using PDCA in the present investigation is attributed through cation exchange mechanism. A calibration plot was constructed by following the standard addition method over the concentration range of 0.25 to 10 ppm of Th in the presence of uranium matrix, which resulted in a linear regression coefficient of 0.9978. The precision of the method was better than 5% and the LOD for Th was found to be 0.1ppm (S/N=3). The method has been validated by comparing the results with the results obtained from ICP-MS analysis where the This separated from the uranium matrix. The proposed method is simple, rapid, accurate and cost effective compared to techniques like ICP-MS or ICP-AES and is suitable for the routine kind of analysis.

Determination of inorganic anions in ethyl acetate by in-line hollow fiber membrane extraction with ion chromatography

In this work, a novel hollow fiber membrane extractor was set up to extract inorganic anions from ethyl acetate using deionized water. Inorganic anions in slightly soluble organic solvents can be determined by the in-line hollow fiber membrane extractor coupled with ion chromatography at first time. Different aspects of the extraction procedure such as magnetic stirring speed, extraction flow rate and extraction time were optimized to achieve high extraction efficiency and good separation results. Satisfactory linear range, limits of detection and good repeatability were obtained. The procedure was applied to analyze inorganic anions in two commercial ethyl acetate samples.

Determination of toluene diisocyanate in synthetic-rubber track by ion chromatography with ultraviolet detection after alkaline suppressor

In the present work, a novel analytical method was proposed for the determination of toluene diisocyanate （TDI） in syntheticrubber track by ion chromatography （IC） coupled with an ultraviolet detector setting at 212 nm. TDI can be hydrolyzed to toluene diamine （TDA） which can be separated by cation-exchange IC easily. The optimum IC separation was performed on an IonPac CS12A column （150 mm ×4.0 mm） using 20 mmol L^-1 sodium sulfate, 10 mmol L^-1 sulfuric acid and 10% acetonitrile as eluent. It was found that a higher signal response of TDA could be obtained under alkaline condition. A suppressor was used to change the acidic eluent into alkaline one. 0.8 mol L^-1 potassium hydroxide was chosen as the optimum regeneration eluent. With the added suppressor and regenerant, signal response was magnified by about 16 times and lower limit of detection （LOD, 0.13 μg L^-1） was obtained. Within-day relative standard deviation （R.S.D.） was less than 3.6%. The recoveries of TDI spiked in synthetic-rubber track samoles were 96.4-110.6%.

Separation of Inorganic Anions Using Methacrylate-Based Monolithic Column Modified with Trimethylamine in Ion Chromatography Capillary System

Methacrylate-based monolithic column was prepared in fused-silica capillary (80 ′ 0.32 mm i.d.) by in situ polymerizetion reaction using glycidyl methacrylate as monomer;ethylene dimethacrylate as crosslinker;1-propanol, 1,4-butanediol, and water as porogenic solvents. The monolith matrix was modified with trimethylamine to create strong anion exchanger via ring opening reaction of epoxy groups. The morphology of the monolithic column was studied by using Scanning Electron Microscope (SEM). This column had good mechanical stability and permeability. The effects of various mobile phases for separation of inorganic anions were investigated. Iodate, bromate, nitrite, bromide, and nitrate were separated within 11 min using100 mMpotassium chloride as mobile phase and detected at 210 nm. This method showed good precision of retention time, acceptable linearity and good sensitivity. Under the optimum condition, the RSD of the retention time was in the range of 1.09%-1.75% (n = 6). The calibration curve showed linear relationships between the peak area and the concentration. The limits of detection (LOD) and the limits of quantitation (LOQ) were between 0.08-0.18 mM and 0.26-0.61 mM, respectively. This method was applied to the determination of inorganic anions in tap water and ground water samples.

Comparison of Binding Parameter Constants between Sevelamer Carbonate Tablets and Renvela Tablets by a Validated Ion Chromatography Method

Sevelamer Carbonate is a crossolinked polymeric amine, it is the active ingredient in Renvela Tablets. Sevelamer Carbonate is indicated for the control of hyperphosphatamiea in patients with end-stage renal disease. The binding parameter constants of Sevelamer Carbonate were determined using the Langmuir approximation for the dosage form at pH 4.0 and 7.0 by Ion Chromatography. An Ion Chromatogrpahy method has been developed to estimate free phosphate in in-vitro phosphate binding study of Sevelamer Carbonate Tablets. The method is selective and capable of detecting phosphate in the presence of placebo matrix. The method has been validated with a lower limit of quantitation of 0.2 mM for Phosphate. A linear response function was established in the range of concentrations 0.2 - 30.0 mM (r > 0.99) for Phosphate. The intra and inter day precision values for Phosphate met the acceptance as per Food and Drug Administrations guidelines. Phosphate was stable in the set of stability studies viz. bench-top and autosampler. The developed method was applied to in-vitro phosphate binding studies of Sevelamer Carbonate Tablets.

Research Progress on the Separation of Alkaloids from Chinese Medicines by Column Chromatography

Alkaloids have a variety of bioactivities and great development value in the fields of pharmaceuticals, cosmetics and health food. Column chromatography is a common method for preparing alkaloids. In this paper, the research status of the separation and purification of alkaloids from Chinese medicines by column chromatography is reviewed, and the factors that influence the refining of alkaloids via a macroporous adsorption resin, ion exchange resin and silica gel are summarized. The thermodynamic and kinetic modeling methods for the static adsorption of adsorbents are also reviewed in this paper. It is suggested that the modeling method of the column chromatography process be deeply studied to establish a more stringent quality control method for sampling liquid and to strengthen the online detection of the chromatography process to improve the refining effect of alkaloids.

Trace-Level Analysis of Hexavalent Chromium in Lake Sediment Samples Using Ion Chromatography Tandem Mass Spectrometry

The analysis of hexavalent chromium, Cr(VI), in soil and sediment samples has been predominantly carried out in materials containing elevated levels. Reliable analysis of trace-level of Cr(VI) in sediment samples remains challenging. Cr(VI) analyses with multipoint calibration and speciated isotope dilution (SID) adapted from U.S. EPA method 6800 were used to measure lower-level Cr(VI) on an ion chromatograph coupled with a tandem mass spectrometer (IC-MS/MS). Lake sediment samples were collected from various locations in Northern Ontario and Cr(VI) was extracted using both alkaline digestion and ethylene diaminetetraacetic acid (EDTA) extraction. Certified reference materials were extracted and analyzed by IC-MS/MS and UV-VIS detection. The SID-MS approach allowed for the quantification of Cr(VI) in samples with concentration levels below 0.5 μg.g-1 wet weight.

Optimal Sample Preservation and Analysis of Cr(VI) in Drinking Water Samples by High Resolution Ion Chromatography Followed by Post Column Reaction and UV/Vis Detection

A recent study by the Environmental Working Group reported the detection of hexavalent chromium (Cr(VI)) in tap water at 31 out of 35 states investigated in the United States. Even though Cr(III) is an essential element for human diet, Cr(VI) is a potential carcinogen. Previous work has clearly identified a linear trend of increasing risk of lung cancer mortality with increasing cumulative exposure to water soluble Cr(VI). Regardless, Cr(VI) is still not regulated or monitored in drinking water in the U.S. There is an existing method (EPA 218.6) for the analysis of Cr(VI), however, this analytical method does not addresses detailed sample preservation techniques and optimization process to achieve lowest detection limit possible. In this study, five buffer solutions with pH of 9 and above were compared to determine the most suitable buffer to preserve Cr(VI) in drinking water samples for an extended period of time. Results showed that the five buffers responded very differently to Cr(VI)-fortified drinking water. The best preserving reagent was found to be Ammonium Hydroxide + Ammonium Sulfate (pH 9.2) and Sodium Carbonate + Sodium Bicarbonate+ Ammonium Sulfate (pH 9.7), whereas a buffer solution with Sodium Hydroxide + Sodium Carbonate (pH 11.5+) resulted in a poor chromatographic resolution. A controlled study with a fortified Cr(III) at 1 ppb was also conducted to ensure no false positive detection of Cr(VI) due to the potential oxidation of Cr(III) during sample storage. The optimal preserving reagent identified from this study was compatible with the existing EPA method 218.6 using ion chroma-tography followed by post column reaction, with a method quantitation limit of 0.020 ppb and matrix spike recovery of ± 10%.

Development and Validation of an Ion Chromatography Method for the Simultaneous Determination of Seven Food Additives in Cheeses

Cheeses are characterized by several chemical-physical properties that make it difficult for the microorganisms growth, consequently. The actual European legislation allows the addition of few food additives in this type of food products. In this work, the entire procedure of extraction, purification, chromatographic separations and quali/quantitative determination of seven food additives (sorbic acid, benzoic acid, lactic acid, acetic acid, nitrites, nitrates and phosphates) was developed and applied for the analysis of different types of cheese (mozzarella, cheese spread, semi-hard and hard cheeses). Through validation procedure it was possible to evaluate the most important validation parameters. Extended calibration curves (r > 0.990) were obtained for all the analyzed compounds. Recovery values ranged from 72.8% to 98.4% and a good repeatability was obtained, with precision levels in the range of 0.03% - 0.11% (n = 6). The potential and feasibility of the method were tested by analysing real samples, such as mozzarella, cheese spread, semi-hard and hard cheeses, confirming that the method is well suited to satisfy the demands for accurate confirmation analyses of seven food additives in cheeses, which is especially valuable in official check analyses and in monitoring schemes.

Dimension-Enhanced Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry Combined with Intelligent Peak Annotation for the Rapid Characterization of the Multiple Components from Seeds of Descurainia sophia

The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a cough and asthma relieving agent.Herein,a dimension-enhanced integral approach,by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(UHPLC/IMQTOF-MS)and intelligent peak annotation,was developed to rapidly characterize the multicomponents from SDS.Good chromatographic separation was achieved within 38 min on a UPLC CSH C18(2.1×100 mm,1.7μm)column which was eluted by 0.1%formic acid in water(water phase)and acetonitrile(organic phase).Collision-induced dissociation-MS^(2)data were acquired by the data-independent high-definition MS^(E)(HDMS^(E))in both the negative and positive electrospray ionization modes.A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume.Moreover,a self-built chemistry library was established,which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS^(E)data.As a result of applying the intelligent peak annotation workflows and further confirmation process,a total of 53 compounds were identified or tentatively characterized from the SDS,including 29 flavonoids,one uridine derivative,four glucosides,one lignin,one phenolic compound,and 17 others.Notably,four-dimensional information related to the structure(e.g.,retention time,collision cross section,MS^(1)and MS^(2)data)was obtained for each component by the developed integral approach,and the results would greatly benefit the quality control of SDS.