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Development and Validation of an Analytical Method for Fungicide Sedaxane Determination in Agricultural Products using LC-MS/MS (LC-MS/MS를 이용한 농산물 중 살균제 Sedaxane의 잔류시험법 개발 및 검증)

  • Cho, Sung Min;Do, Jung-Ah;Park, Shin-Min;Lee, Han Sol;Park, Ji-Su;Shin, Hye-Sun;Jang, Dong Eun;Choi, Young-Nae;Jung, Yong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.1
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    • pp.30-39
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    • 2019
  • An analytical method was developed for the determination of sedaxane in agricultural products using liquid chromatograph-tandem mass spectrometry (LC-MS/MS). The samples were extracted with acetonitrile and partitioned with dichloromethane to remove the interference, and then purified by using silica SPE cartridges to clean up. The analytes were quantified and confirmed by using LC-MS/MS in positive ion mode using multiple reaction monitoring (MRM). The matrix-matched calibration curves were linear over the calibration ranges ($0.001-0.25{\mu}g/mL$) into a blank extract with $r^2$>0.99. For validation, recovery tests were carried out at three different concentration levels (LOQ, 10LOQ, and 50LOQ, n=5) with five replicates performed at each level. The recoveries were ranged between 74.5 to 100.8% with relative standard deviations (RSDs) of less than 12.1% for all analytes. All values were consistent with the criteria ranges requested in the Codex guidelines (CAC/GL 40, 2003) and Food Safety Evaluation Department guidelines (2016). The proposed analytical method was accurate, effective and sensitive for sedaxane determination in agricultural commodities.

Development of Simultaneous Analytical Method for Determination of Isoxaflutole and its Metabolite (Diketonitrile) residues in Agricultural Commodities Using LC-MS/MS (LC-MS/MS를 이용한 농산물 중 Isoxaflutole과 대사산물(Diketonitrile)의 동시시험법 개발)

  • Ko, Ah-Young;Kim, Heejung;Do, Jung Ah;Jang, Jin;Lee, Eun-Hyang;Ju, Yunji;Kim, Ji Young;Chang, Moon-Ik;Rhee, Gyu-Seek
    • The Korean Journal of Pesticide Science
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    • v.20 no.2
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    • pp.93-103
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    • 2016
  • A simultaneous analytical method was developed for the determination of isoxaflutole and metabolite (diketonitrile) in agricultural commodities. Samples were extracted with 0.1% acetic acid in water/acetonitrile (2/8, v/v) and partitioned with dichloromethane to remove the interference obtained from sample extracts, adjusting pH to 2 by 1 N hydrochloric acid. The analytes were quantified and confirmed via liquid chromatograph-tandem mass spectrometer (LC-MS/MS) in positive-ion mode using multiple reaction monitoring (MRM). Matrix matched calibration curves were linear over the calibration ranges ($0.02-2.0{\mu}g/mL$) for all the analytes into blank extract with $r^2$ > 0.997. For validation purposes, recovery studies were carried out at three different concentration levels (LOQ, 10LOQ, and 50LOQ) performing five replicates at each level. The recoveries were ranged between 72.9 to 107.3%, with relative standard deviations (RSDs) less than 10% for all analytes. All values were consistent with the criteria ranges requested in the Codex guideline (CAC/GL40, 2003). Furthermore, inter-laboratory study was conducted to validate the method. The proposed analytical method was accurate, effective, and sensitive for isoxaflutole and diketonitrile determination in agricultural commodities.

Establishment of an Analytical Method for Determination of Fungicide Oxathiapiprolin in Agricultural Commodities using HPLC-UV Detector (HPLC-UVD를 이용한 농산물 중 살균제 Oxathiapiprolin의 잔류분석법 확립)

  • Jang, Jin;Kim, Heejung;Do, Jung Ah;Ko, Ah-Young;Lee, Eun Hyang;Ju, Yunji;Kim, Eunju;Chang, Moon-Ik;Rhee, Gyu-Seek
    • Journal of Food Hygiene and Safety
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    • v.31 no.3
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    • pp.186-193
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    • 2016
  • An analytical method was developed for the determination of oxathiapiprolin in agricultural commodities. Oxathiapiprolin is a new oomycide (fungicide of piperidinyl thiazole isoxazoline class) which controls downy mildew in cucurbits caused by Pseudoperonospora cubensis (oomycete plant pathogen). Agricultural commodities were extracted with acetonitrile and partitioned with dichloromethane to remove the interference, adjusting pH between 9 and 10 by 1 N sodium hydroxide. After purification by silica SPE cartridge to clean up the interference of organic compounds, they were finally quantified by HPLC-UVD (high performance liquid chromatograph ultraviolet detector) using a wavelength at 260 nm and confirmed by LC-MS (liquid chromatograph mass spectrometer) in electro-spray ionization positive ion mode. The standard calibration curve was linear with coefficients of determination ($r^2$) 1.00 over the calibration ranges (0.025-2.5 mg/L). Recoveries were ranged between 86.7 to 112.7%, with relative standard deviations less than 10% at three concentration levels (LOQ, 10LOQ, and 50LOQ) performing five replicates. The overall results were determined and estimated according to the CODEX guidelines (CAC/GL40). The proposed method for determination of oxathiapiprolin residues in agricultural commodities can be used as an official method.

Development of a Simultaneous Analytical Method for Determination of Herbicide Fenquinotrione and KIH-3653-M-2 Residues in Agricultural Crops using LC-MS/MS (LC-MS/MS를 이용한 농산물 중 제초제 fenquinotrione 및 대사산물 KIH-3653-M-2 동시시험법 개발)

  • Park, Ji-Su;Do, Jung-Ah;Lee, Han Sol;Cho, Sung Min;Shin, Hye-Sun;Jang, Dong Eun;Jung, Yong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.3
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    • pp.242-250
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    • 2019
  • An analytical method was developed for the determination of fenquinotrione, a triketone herbicide, in agricultural products. Fenquinotrione was metabolized to KIH-3653-M-2 in plants. Analyte extraction was conducted using 2% formic acid in acetonitrile and cleaned up using a hydrophillic-lipophillic balance (HLB) cartridge. The limits of detection (LOD) and quantification (LOQ) were 0.004 and 0.01 mg/kg, respectively. Matrix-matched calibration curves were linear over the calibration ranges ($0.001{\sim}0.1{\mu}g/mL$) into a blank extract with $r^2>0.99$. The recovery results for fenquinotrione and KIH-3653-M-2 ranged between 81.1 to 116.2% and 78.0 to 110.0% at different concentration levels (LOQ, $10{\times}LOQ$, $50{\times}LOQ$) with relative standard deviation (RSD) less than 4.6%. All values were corresponded with the criteria ranges requested in both the Codex (CAC/GL 40-1993, 2003) and MFDS guidelines (2016). Therefore, the proposed method can be used as an official analytical method for determination of fenquinotrione in the Republic of Korea.

Effect of damage on permeability and hygro-thermal behaviour of HPCs at elevated temperatures: Part 2. Numerical analysis

  • Gawin, D.;Majorana, C.E.;Pesavento, F.;Schrelfer, B.A.
    • Computers and Concrete
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    • v.2 no.3
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    • pp.203-214
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    • 2005
  • In the Part 1 paper (Gawin, et al. 2005) some experimental results concerning micro-structural tests, permeability measurements and stress-strain tests of four types of High Performance Concrete, exposed to elevated temperatures (up to $700^{\circ}C$) are presented and discussed. On the basis of these experimental results parameters of the constitutive relationships describing influence of damage and temperature upon material intrinsic permeability at high temperature were determined. In this paper the effects of various formulations of damage-permeability coupling on results of computer simulations are analysed and compared with the results obtained by means of the previously proposed approach, that does not take into account the thermo-chemical concrete damage directly. Numerical solutions are obtained using the recently developed fully coupled model of hygro-thermal and damage phenomena in concrete at elevated temperatures. High temperature effects are considered by means of temperature and pressure dependence of several material parameters. Based on the mathematical model, the computer code HITECOSP was developed. Material parameters of the model were measured by several European laboratories, which participated in the "HITECO" research project. A model problem, concerning hygro-thermal behaviour and degradation of a HPC structure during fire, is solved. The influence of two different constitutive descriptions of the concrete permeability changes at high temperature, including thermo-chemical and mechanical damage effects, upon the results of computer simulations is analysed and discussed.

Pull-out behaviour of recycled aggregate based self compacting concrete

  • Siempu, Rakesh;Pancharathi, Rathish Kumar
    • Computers and Concrete
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    • v.21 no.3
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    • pp.249-259
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    • 2018
  • The use of recycled aggregate in concrete is gaining much attention due to the growing need for sustainability in construction. In the present study, Self Compacting Concrete (SCC) is made using both natural and recycled aggregate (crushed recycled concrete aggregate from building demolished waste) and performance of recycled aggregate based SCC for the bond behaviour of reinforcement is evaluated. The major factors that influence the bond like concrete compressive strength (Mix-A, B and C), diameter of bar ($D_b=10$, 12 and 16 mm) and embedment length of bar ($L_d=2.5Db$, $5D_b$ and full depth of specimen) are the parameters considered in the present study in addition to type of aggregates (natural and recycled aggregates). The mix proportions of Natural Aggregate SCC (NASCC) are arrived based on the specifications of IS 10262. The mix proportions also satisfy the guidelines of EFNARC. In case of Recycled Aggregate SCC (RASCC), both the natural coarse and fine aggregates are replaced 100% by volume with that of recycled aggregates. These mixes are also evaluated for fresh properties as per EFNARC. The hardened properties like compressive strength, split tensile strength and flexural strength are also determined. The pull-out test is conducted as per the specifications of IS 2770 (Part-1) for determining the bond strength of reinforcement. Bond stress versus slip curves were plotted and a typical comparison of RASCC is made with NASCC. The fracture energy i.e., area under the bond stress slip curve is determined. With the use of recycled aggregates, reduction in maximum bond stress is noticed whereas, the normalised maximum bond stress is higher in case of recycled aggregates. Based on the experimental results, regression analysis is conducted and an equation is proposed to predict the maximum bond stress of RASCC. The equation is in good agreement with the experimental results. The available models in the literature are made use to predict the maximum bond stress and compare the present results.

Evaluation of multi-lane transverse reduction factor under random vehicle load

  • Yang, Xiaoyan;Gong, Jinxin;Xu, Bohan;Zhu, Jichao
    • Computers and Concrete
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    • v.19 no.6
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    • pp.725-736
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    • 2017
  • This paper presents the two-, three-, and four-lane transverse reduction factor based on FEA method, probability theory, and the recently actual traffic flow data. A total of 72 composite girder bridges with various spans, number of lanes, loading mode, and bridge type are analyzed with time-varying static load FEA method by ANSYS, and the probability models of vehicle load effects at arbitrary-time point are developed. Based on these probability models, in accordance to the principle of the same exceeding probability, the multi-lane transverse reduction factor of these composite girder bridges and the relationship between the multi-lane transverse reduction factor and the span of bridge are determined. Finally, the multi-lane transverse reduction factor obtained is compared with those from AASHTO LRFD, BS5400, JTG D60 or Eurocode. The results show that the vehicle load effect at arbitrary-time point follows lognormal distribution. The two-, three-, and four-lane transverse reduction factors calculated by using FEA method and probability respectively range between 0.781 and 1.027, 0.616 and 0.795, 0.468 and 0.645. Furthermore, a correlation between the FEA and AASHTO LRFD, BS5400, JTG D60 or Eurocode transverse reduction factors is made for composite girder bridges. For the two-, three-, and four-lane bridge cases, the Eurocode code underestimated the FEA transverse reduction factors by 27%, 25% and 13%, respectively. This underestimation is more pronounced in short-span bridges. The AASHTO LRFD, BS5400 and JTG D60 codes overestimated the FEA transverse reduction factors. The FEA results highlight the importance of considering span length in determining the multi-lane transverse reduction factors when designing two-lane or more composite girder bridges. This paper will assist bridge engineers in quantifying the adjustment factors used in analyzing and designing multi-lane composite girder bridges.

A Study on DNA Sequences and Mutation of Integrase Region of Korean-type Bovine Leukemia Virus (BLV) pol Gene

  • Kwon, Oh-Sik;Kang, Jung-Soon;Park, Hyun-Jin;Yoo, Min
    • Biomedical Science Letters
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    • v.10 no.1
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    • pp.55-63
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    • 2004
  • Bovine leukemia virus (BLV) is a causative agent for lymphoma disease in cattle including cows worldwide. BLV shares similar virion structure and characteristics with other retroviruses. The pol gene of the BLV genome produced reverse transcriptase (RT) and integrase (IN) for important roles for BLV genome integration into host cell chromosomes that is known to be coded in the 3' side of the BLV pol gene (one third portion). In this study, we have sequenced 978 bp in the 3' side of the BLV pol gene from BLV 10C3 in order to determine the BLV IN region of it. And we compared it to the nucleotide sequences of an Australian BLV isolate. As a result, nucleotide sequences of the IN region of the Korean-type BLV pol gene were mutated at a rate of 3.7%. We can confirm that the typical mutations are such as Arg (AGG) $\rightarrow$ Lys (AAG), Thr (ACG) $\rightarrow$ Met (ATG), Ile (ATT) $\rightarrow$ Val (GTT), Asn (ACC) $\rightarrow$ His (CAC), Phe (TTT) $\rightarrow$ Leu (TTG) and Asn (ACC) $\rightarrow$ Asp (GAC). From the analysis of the sequencing data, we were able to determine the zinc-finger-like "HHCC" motif in the amino terminus of BLV IN, that was H-$X_3$-H-$X_{25}-C-X_2$-C. It was also found the DD35E motif in the IN catalytic domain as D-$X_{56}$-D-$X_{35}$-E. It fits very well to the consensus sequences of retroviral IN as well as HHCC motif.

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Shear-induced structure and dynamics of hydrophobically modified hydroxy ethyl cellulose (hmHEC) in the presence of SDS

  • Tirtaatmadija, Viyada;Cooper-white, Justin J.;Gason, Samuel J.
    • Korea-Australia Rheology Journal
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    • v.14 no.4
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    • pp.189-201
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    • 2002
  • The interaction between hydrophobically modified hydroxyethyl cellulose (hmHEC), containing approximately 1 wt% side-alkyl chains of $C_{16}$, and an anionic sodium dodecyl sulphate (SDS) surfactant was investigated. For a semi-dilute solution of 0.5 wt% hmHEC, the previously observed behaviour of a maximum in solution viscosity at intermediate SDS concentrations, followed by a drop at higher SDS concentrations, until above the cmc of surfactant when the solution resembles that of the unsubstituted polymer, was confirmed. Additionally, a two-phase region containing a hydrogel phase and a water-like supernatant was found at low SDS concentrations up to 0.2 wt%, a concentration which is akin to the critical association concentration, cac, of SDS in the presence of hmHEC. Above this concentration, SDS molecules bind strongly to form mixed micellar aggregates with the polymer alkyl side-chains, thus strengthening the network junctions, resulting in the observed increase in viscosity and elastic modulus of the solution. The shear behaviour of this polymer-surfactant complex during steady and step stress experiments was examined In great detail. Between SDS concentrations of 0.2 and 0.25 wt%, the shear viscosity of the hmHEC-polymer complex network undergoes shear-induced thickening, followed by a two-stage shear-induced fracture or break-up of the network. The thickening is thought to be due to structural rearrangement, causing the network of flexible polymers to expand, enabling some polymer hydrophobic groups to be converted from intra- to inter-chain associations. At higher applied stress, a partial local break-up of the network occurs, while at even higher stress, above the critical or network yield stress, a complete fracture of the network into small microgel-like units, Is believed to occur. This second network rupture is progressive with time of shear and no steady state in viscosity was observed even after 300 s. The structure which was reformed after the cessation of shear is found to be significantly different from the original state.

The origins and evolution of cement hydration models

  • Xie, Tiantian;Biernacki, Joseph J.
    • Computers and Concrete
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    • v.8 no.6
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    • pp.647-675
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    • 2011
  • Our ability to predict hydration behavior is becoming increasingly relevant to the concrete community as modelers begin to link material performance to the dynamics of material properties and chemistry. At early ages, the properties of concrete are changing rapidly due to chemical transformations that affect mechanical, thermal and transport responses of the composite. At later ages, the resulting, nano-, micro-, meso- and macroscopic structure generated by hydration will control the life-cycle performance of the material in the field. Ultimately, creep, shrinkage, chemical and physical durability, and all manner of mechanical response are linked to hydration. As a way to enable the modeling community to better understand hydration, a review of hydration models is presented offering insights into their mathematical origins and relationships one-to-the-other. The quest for a universal model begins in the 1920's and continues to the present, and is marked by a number of critical milestones. Unfortunately, the origins and physical interpretation of many of the most commonly used models have been lost in their overuse and the trail of citations that vaguely lead to the original manuscripts. To help restore some organization, models were sorted into four categories based primarily on their mathematical and theoretical basis: (1) mass continuity-based, (2) nucleation-based, (3) particle ensembles, and (4) complex multi-physical and simulation environments. This review provides a concise catalogue of models and in most cases enough detail to derive their mathematical form. Furthermore, classes of models are unified by linking them to their theoretical origins, thereby making their derivations and physical interpretations more transparent. Models are also used to fit experimental data so that their characteristics and ability to predict hydration calorimetry curves can be compared. A sort of evolutionary tree showing the progression of models is given along with some insights into the nature of future work yet needed to develop the next generation of cement hydration models.