Determination of 13 preservatives in cosmetics by high performance liquid chromatography and verification by mass spectrometry

A method using high performance liquid chromatography(HPLC)was developed for the s imultaneous determination of 13 preservatives(levulinic acid,p-hydroxyacetophenone,raspberry ketone,p-anisic acid,caprylhydroxamic acid,hydroxyethoxyphenyl butanone,methylisothiazolinone,phenoxyethanol,b e n z oic acid,methylparaben,chlorphenesin,dehydroacetic acid,and 5-bromo-5-nitro-1,3-dioxane)in cosmetics.Different types of samples were ultrasonically extracted by methanol,then the separation of 13 preservatives was carried out on a column of Agilent ZORBAX Eclipse XDB-C18(250 mm×4.6 mm,5μm)by gradient elution at a flow rate of 1.0 mL/min,using 0.1%phosphoric acid solution and acetonitrile as mobile phases.The column temperature was 30℃,and the detection was completed by a diode array detector with the wavelengths at 275,230 and 210 nm.Suspected positive samples were further confirmed by liquid chromatography-tandem mass spectrometry or gas chromatography-mass spectrometry.The linear regression analysis data shows good linearity for 13 preservatives in the respective mass concentration range,with their correlation coefficients(r)greater than 0.9998.The limits of detection(LODs)and limits of quantitation(LOQs)of the method are in the ranges of 0.4-100.0 mg/kg and 1.2-250.0 mg/kg,respectively.At three spiked levels,the average recoveries for 13 target compounds in three kinds of matrix samples are within 84.0%-115.4%,and the relative standard deviations(RSD)are within 0.5%-4.8%(n=6).This method is convenient,efficient,and precise,which can be used for qualitative and quantitative analysis of common preservatives in daily cosmetics.

Determination of Benzo[a]pyrene in Edible Oil by High Performance Liquid Chromatography-Fluorescence Detector (HPLC-FL)

In this study, an optimized high performance liquid chromatography-fluorescence detector (HPLC-FL) method for the determination of benzo[a]pyrene in edible oil was established. HPLC was performed with Thermo Fisher Scientific C18 column (250 mm×4.6 mm, 5 μm) as the chromatographic column and acetonitrile and water as the mobile phase, and the excitation wavelength and emission wavelength of fluorescence detector were 286 and 430 nm, respectively. The response was high, and the linear range was 0.5-10.0 ng/ml. The lowest limit of detection was 0.11 ng/ml, and the average recovery was 92.5%. This method is suitable for quantitative analysis of benzo[a]pyrene content in edible oil.

STUDY ON OPTIMIZATION OF HIGH PERFORMANCE CONCRETE ADMIXTURES

Influences of admixtures on the workability and strength of high performance concrete （HPC） are in- vestigated. The types of investigated admixtures include naphthalene series high range water reducing agent, polycarboxlic series high range water reduce agent and sodium sulfate hardening accelerating agent. Two kinds of curing condition, namely steam curing condition and standard curing condition, are adopted. The result shows that HPC, added with polycarboxlic series of high performance water reducer, has high workability and strength, while sodium sulfate accelerating agent causes poor workability and low strength. Thus for vapor-cured HPC and its formulations, naphthalene series high range water reducing agent with less sodium sulfate should be given pri- ority. Therefore, the differences of curing conditions should be considered when selecting HPC admixtures.

High Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometric Analysis of Bilobalide and Ginkgolides in Ginkgo biloba L. Leaves

The ginkgo terpenoids including bilobalide and ginkgolides are the main pharmaceutical components in the leaves or extracts of Ginkgo biloba L. In this paper, the analysis of bilobalide and ginkgolides in leaves of Ginkgo biloba L. by high performance liquid chromatography (HPLC)-electrospray ionization (ESI)-mass spectrometry (MS) was carried out. The separation was performed on Inertsil ODS3 column with methanol-water (36:64) as mobile phase, with 1 mL·min -1 of flow rate at 35℃. Then the mass spectrum analysis was conducted by ZMD micromass electrospray ionization (ESI)-mass spectrometer (MS). The HPLC total ion chromatogram and selected ion chromatogram (with 325, 407, 423, 439 of m/z) of the sample and ESI-/MS mass spectra of the peaks in the chromatograms were obtained. So bilobalide, ginkgolide A, B, C and J in Ginkgo biloba L. leaves were identified. The method is easy and rapid, with a good accuracy.

High Performance 70nm CMOS Devices

A high performance 70nm CMOS device has been demonstrated for the first time in the continent, China. Some innovations in techniques are applied to restrain the short channel effect and improve the driving ability, such as 3nm nitrided oxide, dual poly Si gate electrode, novel super steep retrograde channel doping by heavy ion implantation, ultra shallow S/D extension formed by Ge PAI(Pre Amorphism Implantation) plus LEI(Low Energy Implantation), thin and low resistance Ti SALICIDE by Ge PAI and special cleaning, etc. The shortest channel length of the CMOS device is 70nm. The threshold voltages, G m and off current are 0 28V,490mS·mm -1 and 0 08nA/μm for NMOS and -0 3V,340mS·mm -1 and 0 2nA/μm for PMOS, respectively. Delays of 23 5ps/stage at 1 5V, 17 5ps/stage at 2 0V and 12 5ps/stage at 3V are achieved in the 57 stage unloaded 100nm CMOS ring oscillator circuits.

An Improved High Fan-in Domino Circuit for High Performance Microprocessors

An improved high fan-in domino circuit is proposed. The nMOS pull-down network of the circuit is divided into several blocks to reduce the capacitance of the dynamic node and each block only needs a small keeper transistor to maintain the noise margin. Because we omit the footer transistor, the circuit has better performance than the standard domino circuit. A 64-input OR-gate implemented with the structure is simulated using HSPICE under typical conditions of 0.13μm CMOS technology. The average delay of the circuit is 63.9ps, the average power dissipation is 32.4μW, and the area is l15μm^2. Compared to compound domino logic, the proposed circuit can reduce delay and power dissipation by 55% and 38%, respectively.

Determination of trans-resveratrol in mouse liver by high performance liquid chromatography

To develop a sensitive high performance liquid chromatography （HPLC） assay for the determination of trans-resveratrol in mouse liver. The whole liver of a mouse was removed from the body, homogenated, and extracted by ethyl acetate. The organic layer was isolated and evaporated to dryness, the residue was reconstituted in 0.2 mL mobile phase for centrifugation, and 50 uL of the supernatant was injected into the/-IPLC instrument. The sample was separated on a Shimadzu ODS column （150 mm × 4.6 mm, 5 um） at 35 ℃ and detected by ultraviolet （UV） detector at the wavelength of 305 nm. The mobile phase consisted of methanol and 0.1 mol/L acetic acid （4：6, v/v） with the flow-rote at 1 mL/min. The limit of detection was 3.0 ng/g in liver homogenate with a signal/noise ratio of 3：1. The linear range of the calibration curve was 5.0-120.0 ng/g. The mean recoveries at the concentrations of 6, 10 and 80 ng/g were 102%, 96.0% and 91.5%, respectively. The RSDs for inter- and intra-day assays were less than 5%. Compared with other reported methods, this method was faster and more sensitive. It was also proved to be of good linearity, selectivity, accuracy and precision, and can be efficiently applied to the pharmacoldnetic study of trans-resveratrol in mouse liver.

Analysis of ganciclovir and its related substances using high performance liquid chromatography and liquid chromatography-mass spectrometry methods

Objective High performance liquid chromatography(HPLC)and liquid chromatography-mass spectrometry(LC/MS)methods were developed for the determination of ganciclovir and its related substances.Methods A Hypersil ODS2 column(4.6 mm×250 mm,5 μm)was used with a mobile phase of 0.02 M potassium dihydrogen phosphate buffer(pH 6.0)-methanol(92∶8)at a flow rate of 1.0 mL/min,and UV detector set at 254 nm was used for monitoring the eluents.Results The method was simple,rapid,selective and capable of separating all related substances at trace level with a detection limit of 0.04 μg/mL.It has been validated with respect to accuracy,precision,linearity,and limits of detection and quantification.The linearity range was 10.2-153.0 μg/mL with r=0.9998.The percentage recoveries ranged from 96.7% to 101.6%,and RSD was 1.24%-1.96%(n=5).Conclusion The method was found to be suitable not only for monitoring the reactions during the process development but also for quality control of ganciclovir.For identification of related substances,LC/MS was used.The mainly related substances of ganciclovir active pharmaceutical ingredients(API)were determined as guanine,(1,3-dioxolan-4-yl)methyl acetate,and diacetyl guanine.

INFLUENCE OF AIRCRAFT DEICER ON FREEZE-THAW DURABILITY OF HIGH PERFORMANCE CONCRETE

The influence of glycol,the main composition of the most frequently used aircraft dicer,on the freeze-thaw durability of high performance concrete（HPC）is investigated.Freeze-thaw durability of HPC is tested by accelerated freeze-thaw test.Four kinds of the solution,i.e.,tap water,3.5% NaCl solution,glycol solutions,and a LBR-A type commercial aircraft deicer are employed.Results show that freeze-thaw durability of HPC exposed to glycol solutions is closely related to the solution concentrations.The failure of HPC exposed to 3.5% glycol solution is similar to that of those exposed to 3.5% NaCl solution,i.e.,serious surface scaling.While the damage of HPC exposed to 12.5%—25% glycol solutions is postponed.Compared with glycol solution,the commercial aircraft deicer has much more negative effects on HPC freeze-thaw durability compared with 3.5% NaCl solution.In the presence of commercial aircraft deicer for HPC subjected to freeze-thaw cycles,the deterioration is mainly due to scaling and spalling.

Detection of 36 antibiotics in coastal waters using high performance liquid chromatography-tandem mass spectrometry

Among pharmaceuticals and personal care products released into the aquatic environment, antibiotics are of particular concern, because of their ubiquity and health effects. Although scientists have recently paid more attention to the threat of antibiotics to coastal ecosystems, researchers have often focused on relatively few antibiotics, because of the absence of suitable analytical methods. We have therefore developed a method for the rapid detection of 36 antibiotic residues in coastal waters, including tetracyclines （TCs）, sulfanilamides （SAs）, and quinolones （QLs）. The method consists of solid-phase extraction （SPE） and liquid chromatography-tandem mass spectrometry （LC-MS/MS） analysis, using electrospray ionization （ESI） in positive mode. The SPE was performed with Oasis HLB and Oasis MCX cartridges. Chromatographic separation on a Cr8 column was achieved using a binary eluent containing methanol and water with 0.1% formic acid. Typical recoveries of the analytes ranged from 67.4% to 109.3% at a fortification level of 100 ng/L. The precision of the method, calculated as relative standard deviation （RSD）, was below 14.6% for all the compounds. The limits of detection （LODs） varied from 0.45 pg to 7.97 pg. The method was applied to detemaine the target analytes in coastal waters of the Yellow Sea in Liaoning, China. Among the tested antibiotics, 31 were found in coastal ＇waters, with their concentrations between the LOD and 212.5 ng/L. These data indicate that this method is valid for analysis of antibiotics in coastal waters. The study first reports such a large number of antibiotics along the Yellow Sea coast of Liaoning, and should facilitate future comprehensive evaluation of antibiotics in coastal ecosystems

Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

A novel method for the determination of five carbamate pesticides （metolcarb, carbofuran, carbaryl, isoprocard and diethofencard） in water samples was developed by dispersive liquid-liquid microextraction （DLLME） coupled with high performance liquid chromatography-diode array detector （HPLC-DAD）. Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results. Under the optimum conditions for the method, the calibration curve was linear in the concentration range from 5 to 1000 ng mL^-1 for all the five carbamate pesticides, with the correlation coefficients （r^2） varying from 0.9984 to 0.9994. Good enrichment factors were achieved ranging from 80 to 177- fold, depending on the compound. The limits of detection （LODs） （S/N = 3） were ranged from 0.1 to 0.5 ng mL^-1. The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

Combined effect of steel fibres and steel rebars on impact resistance of high performance concrete

The impact properties of normal concrete (NC) and reinforced concrete (RC) specimens,steel fibre reinforced concrete (SFRC) specimens and RC+SFRC specimens with different steel fibre dosages were investigated with the drop-weight impact test recommended by ACI Committee 544.The results indicate that the number of blows to final failure is greatly increased by addition of steel fibres.Moreover,the combination of steel fibres and steel rebars demonstrates a significant positive composite effect on the impact resistance,which results in the improvement in impact toughness of concrete specimens.In the view of variation of impact test results,the two-parameter Weibull distribution was adopted to analyze the experimental data.It is proved that the probabilistic distributions of the blows to first crack and to final failure of six types of samples approximately follow two-parameter Weibull distribution.

Looking Ahead——A New Generation of High Performance Refractory Ceramics

It is expected that in the new century, to cope with developments of new high temperature technologies , a new generation of high performance refractory ceramics will e-merge and flourish which should include the following (1) oxide and nonoxide composites characterized by a unique combination of high hot strength , high thermal shock resistance and high corrosion resistance ; (2) free CaO bearing basic refractories capable of purifying molten metal for improving cleanliness and of absorbing contaminants from waste gases for reducing environmental pollution ; (3) free flowing zero cement castables with improved thermome-chanical properties , thermal shock resistance and corrosion resistance and gradient castables with varying matrix composition and varying texture.

Comparison of protocatechuic aldchyde in Radix Salvia miitiorrhiza and corresponding pharmacological sera from normal and fibrotic rats by high performance liquid chromatography

AIM： To observe the effect of protocatechuic aldchyde on the proliferation of hepatic stellate cells （HSCs）. METHODS： Liver fibrosis was induced in rats by carbon tetrachloride （CCh）. Then normal and fibrotic drug sera were extracted from rats. The effects of protocatechuic aldchyde, raw Radix Salvia miltiorrhiza and drug sera of Salvia miltiorrhiza on HSC growth were determined by CCKoS. The protocatechuic aldchyde was separated by high performance liquid chromatography （HPLC） in a AIItima C18 column （250 mm × 4.6 mm, 5 μm） with a mobile phase of acetonitrile-4% glacial acetic acid solution （gradient elution） at the wavelength of 281 nm. RESULTS： Protocatechuic aldchyde, raw Radix Salvia miltiorrhiza and drug sera of Salvia miltiorrhiza were found to have inhibitory effects on proliferation of rat HSCs. Raw Radix Salvia miltiorrhiza had a stronger inhibitory effect than the drug sera. The fibrotic drug sera showed a higher suppressive effect than the normal drug sera （P 〈 0.05）. Protocatechuic aldchyde was found in crude materials of both Radix Salvia miltiorrhiza and its corresponding drug sera. The average recovery （n = 6） was 110.5% for raw Salvia miltiorrhiza Bge, 102% for normal drug sera and 105.2% for fibrotic drug sera. The relative standard devitation （RSD） was 0.37%, 1.96% and 1.51%, respectively （n=6）. The contents of protocatechuic aldchyde were 0.22%, 0.15% and 0.19%, respectively （n = 6） （P〈 0.05）. The RSD was 0.33%, 0.75% and 1.24% （n=6） for raw material of Radix Salvia miltiorrhiza, normal drug sera and fibrotic drug sera, respectively. The samples were stable for 6 d. CONCLUSION： Protocatechuic aldchyde can inhibit the growth of HSCs. HPLC is suitable for the determination of virtual bioactive components of Chinese herbal medicines in vitro.

Determination of Organic Acids in Root Exudates by High Performance Liquid Chromatography: I. Development and Assessment of Chromatographic Conditions *1

Methods for determining nine low molecular weight organic acids in root exudates were developed by using reversed phase high performance liquid chromatography with UV (ultraviolet) detection at 214 nm. The mobile phase was 18 mmol L -1 kH 2PO 4 adjusted to pH 2.25 with phosphoric acid and the flow rate was 0.3 mL min -1 . The analytical column was a reversed phase silica based C 18 column (Shim pack CLC ODS). The root exudates were collected through submerging the whole root system into aerated deionized water for 2 hours. The filtered exudate solutions were concentrated to dryness by rotary evaporation at 40 °C, dissolved in 10 mL mobile phase. The chromatographic conditions of organic acid determination were analyzed. The results showed that there was a high selectivity and sensitivity in the organic acid determination by reversed phase high performance liquid chromatography. Coefficients of variation for organic acid determination were lower than 10% except lactic acid. The recoveries were consistently between 80.1% to 108.3%. Detection limits were approximately 0.05 to 4.5 mg L -1 for organic acids except succinic acid with the detection limit of 7.0 mg L -1 . Phosphorus deficiency may contribute to the release of organic acids in soybean root exudates especially malic, lactic and citric acids.

Carbonation Resistance of Sulphoaluminate Cement-based High Performance Concrete

The influences of water/cement ratio and admixtures on carbonation resistance of sulphoaluminate cement-based high performance concrete （HPC） were investigated. The experimental results show that with the decreasing water/cement ratio, the carbonation depth of sulphoaluminate cement-based HPC is decreased remarkably, and the carbonation resistance capability is also improved with the adding admixtures. The morphologies and structure characteristics of sulphoaluminate cement hydration products before and after carbonation were analyzed using SEM and XRD. The analysis results reveal that the main hydration product of sulphoaluminate cement, that is ettringite （AFt）, decomposes after carbonation.

Simultaneous determination of three curcuminoids in Curcuma longa L.by high performance liquid chromatography coupled with electrochemical detection

A novel method for analysis of three active components curcumin, demethoxycurcumin and bisdemethoxycurcumin in Curcuma longa L. was developed by HPLC coupled with electrochemical detection. Three curcuminoids were well separated on a C18 column and detected with high sensitivity. A mobile phase containing acetonitrile and 10 mM Na2HPO4-H3PO4 （pH 5.0） （50：50, v/v） was used. Good linearity was obtained in the range of 0.208-41.6, 0.197-39.4, and 0.227-114μM for curcumin, demethoxycurcumin and bisdemethoxycurcumin respectively. The limit of detection reached up to 10 ？ 8 M, which was lower than that by UV detection. The relative standard deviations （RSDs） ranged from 1.06%to 1.88%for intra-day precision and from 4.30%to 5.79%for inter-day precision, respectively. The proposed method has been applied in real herb sample and recoveries ranging from 86.3%to 111%were obtained.

Simultaneous determination of 12,13-dihydroxyeuparin and glycyrrhizic acid in Yanyanfang mixture by high performance liquid chromatography

A reversed phase high performance liquid chromatography （HPLC） method was established for the simultaneous determination of 12, 13-dihydroxyeuparin and glycyrrhizic acid in Yanyanfang mixture. A Grace Apollo Cl8 column （250 mm × 4.6 mm, 5 μm） was used as the stationary phase and the mobile phase was composed of acetonitrile and aqueous phosphoric acid （0.2%, v/v）. Gradient elution was carried out at the flow rate of 1.0 mL/min and the column temperature was 30 ℃. An ultraviolet （UV） detector was used with a selected wavelength of 240 nm. Calibration curves were linear within the concentration range of 4.6-45.75 μg/mL for 12, 13-dihydroxyeuparin （r〉0.9999） and 106.9-1068.9μg/mL for glycyrrhizic acid （r〉0.9999）, respectively. Recoveries were 102.18% for 12, 13-dihydroxyeuparin and 101.17% for glycyrrhizic acid. The method developed could be applied to the simultaneous determination of 12, 13- dihydroxyeuparin and glycyrrhizic acid in Yanyanfang mixture.

Pore Size Distribution of High Performance Metakaolin Concrete

The Compressive strength, porosity and pore size distribution of high performance metakaolin (MK) concrete were investigated. Concretes containing 0,5% , 10% and 20% metakaolin were prepared at a water / cementitious material ratio ( W/C) of 0. 30. In parallel, concrete mixtures with the replacement of cement by 20% fly ash or 5 and 10% silica fume were prepared for comparison. The specimens were cured in water at 27℃ for 3 to 90 days. The results show that at the early age of curing (3 days and 7 days), metakaolin replacements increase the compressive strength, but silica fume replacement slightly reduces the compressive strength. At the age of and after 28 days , the compressive strength of the concrete with metakaolin and silica fume replacement increases. A strong reduction in the total porosity and average pore diameter were observed in the concrete with MK 20% and 10% in the first 7 days.

High Performance Concrete and Its Typical Mixes

With the modern development of chemical and mineral admixtures, it is now possible to produce much higher performance concrete than before. Higher performance does not only mean higher strength, but also better durability, lower risk of thermal cracking and higher dimensional stability etc. The three most effective admixtures for producing high performance concrete are superplastieizer, pulverized fuel ash and condensed silica fume. This paper outlines the properties of these materials and presents some practical guidelines for their usage.