• Mass Spectrometry Letters
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• 제8권3호
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• pp.59-64
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• 2017

In clinical diagnosis, it's well known that the abnormal level of uric acid (UA) in human body is implicated in diverse human diseases, for instance, chronic heart failure, gouty arthritis, diabetes, and so on. As a primary method, an isotope dilution mass spectrometry (IDMS) has been used to obtain the accurate quantity of UA in blood or serum and also develop the certificated reference material (CRM) so as to provide a SI-traceability to clinical laboratories. Due to the low solubility of UA in water, an ammonium hydroxide ($NH_4OH$) has been considered as a promising solvent to increase the solubility of UA that enables the preparation of both UA and its isotope standard solution for next IDMS-based absolute quantification. But, because of using this $NH_4OH$ solvent, it gives rise to the unwanted degradation of UA. In this study, we sought to optimize condition for the stability of UA in $NH_4OH$ solution by varying the mole ratios of UA to $NH_4OH$, followed by ID-LC-MRM analysis. In addition, we also inspected minutely the effect of the storage temperatures. Additionally, we also performed the quantitative analysis of UA in the KRISS serum certificated reference material (CRM, 111-01-02A) with diverse mixing ratios of UA to $NH_4OH$ and then compared those values to its certification value. Based on our experiments, adjusting the mole ratio of 1/2 ($UA/NH_4OH$) with the storage temperature of $-20^{\circ}C$ is an effective way to secure both the solubility and stability of UA in $NH_4OH$ solution for next IDMS-based quantification of UA in serum.

• 분석과학
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• 제18권4호
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• pp.271-277
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• 2005

혈액 내 urea는 임상진단 시 신장 기능을 판단하는 중요한 표지물질로서 측정되고 있다. 단백질 등 질소화합물의 최종 대사물인 urea는 콩팥의 사구체에서 걸러져 소변으로 배출되는데, 사구체의 거르는 능력이 저하되면 결국 혈액 속의 urea 농도가 증가하게 되어 신장 기능의 정상여부를 판단할 수 있게 된다. 이러한 임상진단 결과의 신뢰성 향상을 위해서는 측정결과가 일차분석법으로 인증된 인증표준 물질과 소급성 고리를 유지해야 한다. 본 연구에서는 혈청 내 urea의 일차분석법으로서 $15^N_2$-urea를 내부 표준물질로 사용하는 동위원소희석 액체크로마토그라피-질량분석법 (ID-HPLC/MS)을 개발하였다. 이 방법은 측정원리상 고도의 정확성이 확보될 뿐 아니라 별도의 유도체화가 필요 없기 때문에 빠르고 편리하다. $C_{18}$-분리관에 0.1 mmol/L $NH_4Cl$ buffer를 이동상으로 사용하여 urea를 분리하였는데, 이 완충용액은 비교적 분자량이 작은 urea를 질량분석하는데 방해가 크지 않은 장점이 있다. HPLC와 질량분석기의 인터페이스로서 positive mode의 electrospray ionization (ESI)를 사용하여 높은 감도와 재현성을 성취하였다. 국제적으로 인정된 인증표준물질의 분석을 통해 최적화된 방법의 유효성을 확인하였으며, 국제비교시험에도 참여하여 좋은 결과를 얻었다. ISO guide에 따라 불확도를 계산하였으며, 확장 불확도는 95% 신뢰도에서 약 1.8%로 나타났다. 이 분석법은 표준연에서 개발 중인 혈청인증표준물질을 인증하는 일차기준측정절차로도 사용되고 있다.

• Asian-Australasian Journal of Animal Sciences
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• 제20권6호
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• pp.894-899
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• 2007

An experiment was conducted using a [6, 6-$^2H$]glucose isotope dilution method to determine the effects of plantain (Plantago lanceolata L.) on plasma glucose metabolism in sheep taken from a thermoneutral environment and exposed to a hot environment. The sheep were fed either mixed hay (MH) of orchardgrass (Dactylis glomerata L.) and reed canarygrass (Phalaris arundinacea L.) at a 60:40 ratio or MH and plantain (PL) at a 9:1 ratio in a crossover design for each 23-day period. In both dietary treatments the metabolizable energy (ME) and crude protein intake were designed to be isoenergetic and isoproteinous at around maintenance level. The sheep were taken from a thermoneutral environment ($20^{\circ}C$, 70% RH) and exposed to a hot environment ($28-30^{\circ}C$, 70% RH) for 5 days. The isotope dilution method using a single injection of [6, 6-$^2H$]glucose was performed on the $18^{th}$ day of the thermoneutral environment and on the $5^{th}$ day of heat exposure. Plasma glucose pool size was numerically lower (p = 0.26) during heat exposure on both dietary treatments, and numerically higher (p = 0.13) on the MH diet irrespective of environmental temperature. Plasma NEFA concentration (p = 0.01) and glucose turnover rate (p = 0.03) were decreased during heat exposure, but remained similar between diets. It could be concluded that, although no positive impact of plantain on glucose metabolism was found under the present experimental conditions (plantain constituted only 10% of basal diet), plantain herb is an alternative to MH for rearing sheep in both thermoneutral and hot environments.

• Asian-Australasian Journal of Animal Sciences
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• 제29권4호
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• pp.523-529
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• 2016

An isotope dilution method using $[U-^{13}C]glucose$ and $[1-^{13}C]leucine$ (Leu) was conducted to evaluate the effects of rice straw supplemented with urea and molasses (RSUM-diet) on plasma glucose and Leu turnover rates in sheep. Nitrogen (N) balance, rumen fermentation characteristics and blood metabolite concentrations were also determined. Four sheep were fed either mixed hay (MH-diet), or a RSUM-diet with a crossover design for two 21 days period. Feed allowance was computed on the basis of metabolizable energy at maintenance level. The isotope dilution method was performed as the primed-continuous infusion on day 21 of each dietary period. Nitrogen intake was lower (p = 0.01) for the RSUM-diet and N digestibility did not differ (p = 0.57) between diets. Concentrations of rumen total volatile fatty acids tended to be higher (p = 0.09) for the RSUM-diet than the MH-diet. Acetate concentration in the rumen did not differ (p = 0.38) between diets, whereas propionate concentration was higher (p = 0.01) for the RSUM-diet compared to the MH-diet. Turnover rates as well as concentrations of plasma glucose and Leu did not differ between diets. It can be concluded that kinetics of plasma glucose and Leu metabolism were comparable between the RSUM-diet and the MH-diet, and rumen fermentation characteristics were improved in sheep fed the RSUM-diet compared to the MH-diet.

• Bulletin of the Korean Chemical Society
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• 제34권6호
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• pp.1698-1702
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• 2013

Glucose is a common medical analyte measuring in human serum or blood samples. The development of a primary method is necessary for the establishment of traceability in measurements. We have developed an isotope dilution liquid chromatography tandem mass spectrometry as a primary method for the measurement of glucose in human serum. Glucose and glucose-$^{13}C_6$ in sample were ionized in ESI negative mode and monitored at mass transfers of m/z 179/89 and 185/92 in MRM, respectively. Glucose was separated on $NH_2P$-50 2D column, and the mobile phase was 20 mM $NH_4OAc$ in 30% acetonitrile/70% water. Verification of this method was performed by the comparison with NIST SRMs. Our results agreed well with the SRM values. We have developed two levels of glucose serum certified reference material using this method and distributed them to the clinical laboratories in Korea as samples for proficiency testings. The expended uncertainty was about 1.2% on 95% confidence level. In proficiency testings, the results obtained from the clinical laboratories showed about 3.6% and 3.9% RSD to the certified values. Primary method can provide the traceability to the field laboratories through proficiency testings or certified reference materials.

• Nuclear Engineering and Technology
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• 제38권3호
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• pp.301-310
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• 2006

Destructive methods were used for the burnup determination of U-Zr alloy nuclear fuel irradiated in the High-flux Advanced Neutron Application Reactor (HANARO) at KAERI. The dissolution rate of unirradiated U-Zr alloy fuel in $HNO_3$/HF mixtures was investigated for the experimental conditions of a different temperature, and initial concentrations of HF and $HNO_3$. The irradiated U-Zr alloy fuel specimen was dissolved in a mixed acid condition of 3 M HNO3 and 1 M HF at $90^{\circ}C$ for 8 hours under reflux. The total burnup was determined from measurement of the Nd isotope burnup monitors. The method includes U, Pu, $^{148}Nd,\;^P{145}Nd+^{146}Nd,\;^{144}Nd+^{143}Nd$ and total Nd isotopes determination by the isotope dilution mass spectrometric method (IDMS) using triple spikes $(^{233}U,\;^{242}Pu\;and\;^{150}Nd)$. The effective fission yield was calculated from the weighted fission yields averaged over the irradiation period. The results are compared with that obtained by the destructive -spectrometric measurement of the $^{137}Cs$ monitor.

• 대한화학회지
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• 제55권3호
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• pp.472-477
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• 2011

팔중극자 반응셀 유도결합플라즈마 질량분석법(ORC ICPMS; Octapole Reaction Cell Inductively Coupled Plasma Mass Spectrometry)에서 동위원소 희석법을 이용하여 곡류 중의 셀레늄을 정확히 분석하였다. 충돌기체는 헬륨보다 수소가 더 효율적이었고 최적 흐름속도는 4.0 mL $min^{-1}$ 이었다. ORC는 다원소 이온화학종들의 간섭을 충분히 제거하였으나 시료매트릭스에 브롬이 존재하는 경우, 충돌기체인 $H_2$에 의해 $BrH^+$가 생성되어 m/z 80, 82에 방해를 주었다. 브롬의 화학적 제거는 매우 어려웠으며 $^{82}Se$의 신호세기에 대한 수학적 보정을 사용하고 동위원소 희석법을 적용하였다. 정확도를 검증하기 위하여 표준검정 물질(NIST SRM 1566, 1567)을 분석한 결과, 좋은 일치도를 얻었고, 이를 바탕으로 실제시료인 곡류 중의 셀레늄을 분석하여 계산한 결과, 백미 $0.034{\pm}0.001\;{\mu}g\;g^{-1}$, 현미 $0.059{\pm}0.002_5\;{\mu}g\;g^{-1}$, 흑미 $0.029{\pm}0.001_4\;{\mu}g\;g^{-1}$ 그리고 보리 $0.034{\pm}0.002{\mu}g\;g^{-1}$를 얻었다. 셀레늄 분석에 대한 검출한계($3\sigma$)는 $0.012\;ng\;g^{-1}$ 이었다.

• 분석과학
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• 제19권1호
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• pp.1-8
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• 2006

$1000{\mu}g/g$ 염소 표준용액 중 미량 브롬 불순물 분석을 위해 동위원소희석 질량분석법을 이용하였다. 염소 표준용액 제조에는 비교적 불순물이 적은 KCl 염이 사용되었기 때문에 고농도의 염소 표준용액 중 미량 브롬 불순물 분석은 다량의 K와 Cl 매질로 인한 분광간섭 및 매질효과로 인해 측정이 어렵다. 따라서 브롬을 고농도의 공존원소로부터 분리하기 위해 AG2-X8의 음이온교환수지를 사용하였으며, 브롬 측정 시 ICP-MS의 RF power는 1500 W로 올리고 운반기체유량은 0.77 L/min로 내려서 $ArArH^+$분자이온에 의한 바탕값을 낮추었다. $1000{\mu}g/g$ 염소 표준용액 중 불순물 브롬을 표준물 첨가법으로 분석한 결과는 43.7 ng/g이며, 이온교환수지 처리과정의 재현성 문제로 인한 불확도를 줄이기 위해 동위원소희석법을 사용하여 측정한 결과는 41.2 ng/g(RSD 1.6%)로서 잘 일치하였다.

• Nuclear Engineering and Technology
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• 제33권4호
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• pp.375-385
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• 2001

The total burnup in the spent U$_3$Si/Al fuel samples from Hanaro reactor was determined by destructive methods using $^{148}$ Nd, the sum of $^{143}$ Nd and $^{144}$ Nd, the sum of $^{145}$ Nd and $^{146}$ Nd, and the sum of total Nd isotopes($^{143}$ Nd, $^{144}$ Nd, $^{145}$ Nd, $^{146}$ Nd, $^{148}$ Nd and $^{150}$ Nd) monitors. The fractional($^{235}$ U) turnup in the spent fuel samples was also determined by U and Pu mass spectrometric method. The samples were dissolved in a mixture of 4 M HCI and 10 M HNO$_3$ without any catalyst. The separation of U, Pu and Nd from the spiked and unspiked sample solutions was achieved by two sequential anion exchange separation methods. The isotope compositions of these elements, after their separation from the fuel samples were measured by mass spectrometry. The contents of the elements in the spent fuel samples were determined by isotope dilution mass spectrometric method(IDMS) using $^{233}$ U, $^{242}$ Pu and $^{150}$ Nd as spikes. The effective fission yield was calculated from the weighted fission yields averaged over the irradiation period. The difference between total turnup values determined by various Nd monitors were in the range of 1.8%.

• 분석과학
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• 제25권1호
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• pp.25-32
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• 2012

동위원소희석 액체크로마토그래피-탄뎀질량분석법을 이용하여 차음료 중의 소르빈산을 정밀하게 측정하는 방법을 개발하였다. 소르빈산의 동위원소, $^{13}C_2$-소르빈산은 주문합성하여 구입하였다. 질량 분석기는 음이온 모드로 선택반응분석법 (Selected Reaction Monitoring mode)에서 수행하여, $[M-H]^-$ 이온이 $[M-CO_2H]^-$ 조각이온으로 가는 m/z 111 ${\rightarrow}$ 67와 $^{13}C_2$-소르빈산 m/z 113 ${\rightarrow}$ 68 채널을 선택하여 분석하였다. 분리는 C18 컬럼으로 수행되었으며, 암모니움 아세테이트용액(pH 4.5) 55%와 메탄올 45%로 이동상을 구성하였다. 반복성과 재현성을 포함한 방법의 유효성 검토를 위하여 본 연구원에서 차음료에 소르빈산을 강화하여 균질성있는 기준물질을 제조하였다. 반복성과 재현성 결과는 동위원소희석 액체크로마토그래피-탄뎀질량분석법에 의한 소르빈산의 분석이 신뢰할만 하며 재현성 있는 방법임을 보여주었고, 기준물질들의 소르빈산의 농도는 3.8%의 표준편차를 보여주었다.