一次性使用输液器输注盐酸头孢替安过程中可沥滤物的气相色谱-质谱研究

通过模拟临床使用一次性输液器输注盐酸头孢替安,对一次性使用输液器中可沥滤物进行了气相色谱-质谱分析。研究使用了两个不同厂家生产的A、B两种型号的一次性使用输液器,其中A型输液器中检出环己酮、2-乙基己醇,浓度分别达到了5.166μg/mL和0.4716μg/mL;B型输液器中检出环己酮、2-乙基己醇和2-苯基-2-丙醇,浓度分别达到了3.741μg/mL、0.0827μg/mL和0.1939μg/mL。另外,两种型号的一次性使用输液器中均检出少量邻苯二甲酸(2-乙苯已基)酯(DEHP)溶出,其溶出量分别为0.97μg/set和1.05μg/set。     

Ru~(3+)增敏的化学发光新体系测定呋塞米的研究

Ru~(3+)存在下,呋塞米能够大幅度增强三(1,10-菲咯啉)钌(Ⅱ)(Ru(phen)_3~(2+))-Ce(Ⅳ)体系的化学发光,且当体系中Ru~(3+)的浓度从0增至15μmol/L时,呋塞米对体系发光的增强值提高1个数量级,基于此,建立了高灵敏测定呋塞米的Ru(phen)_3~(2+)-Ce(Ⅳ)-Ru~(3+)体系化学发光方法。在优化实验条件下,该法测定呋塞米的线性范围为5. 0×10~(-9)~2. 0×10~(-6)mol/L,检出限为3. 8×10~(-9)mol/L。方法具有较高的分析灵敏度,将其应用于呋塞米片剂和呋塞米注射液的分析,结果满意。结合紫外光谱的研究结果,对化学发光反应机理进行了探讨。     

甲基磺酸镧催化合成柠檬酸三（2-乙基）己酯的研究

PVC塑料助剂的主增塑剂邻苯二甲酸酯类在过去几十年得到了广泛的应用[1],近年来研究发现,这类增塑剂用于食品包装材料、玩具等可诱发致癌,特别是对婴儿和儿童的生长和发育影响更大[2-3]。柠檬酸酯系列增塑剂具有无毒、生物降解性好、挥发性小、抗细菌,增塑效率高等优点,被FDA认     

顶空固相微萃取/气相色谱法测定聚氯乙烯玩具在模拟唾液浸泡液中多种邻苯二甲酸二酯的溶出量

采用以溶胶-凝胶技术涂渍的富勒烯固相微萃取纤维头,利用顶空固相微萃取/气相色谱法对聚氯乙烯(PVC)塑料玩具在模拟人体唾液浸泡液中邻苯二甲酸二酯类化合物的溶出量进行了测定,并对模拟人体唾液中5种邻苯二甲酸二酯类增塑剂的固相微萃取时间、萃取温度、盐效应、热解吸时间、振荡速度等条件进行优化,研究了PVC塑料玩具在模拟人体唾液中的浸泡条件对增塑剂溶出量的影响。该方法目标化合物的检出限为0.079-1.7 μg/L,回收率为88.4-107.7%(RSD＜8%)。应用于实际玩具样品的分析,结果令人满意。对以溶胶     

气相色谱法测定中、长链脂肪乳注射液中大豆油和中链甘油三酸酯含量的不确定度评定

建立气相色谱法测定中、长链脂肪乳注射液中大豆油和中链甘油三酸酯含量的不确定度评定方法。建立数学模型，分析气相色谱法测定中、长链脂肪乳注射液中大豆油和中链甘油三酸酯含量的不确定度来源及影响因素，对各不确定度分量进行评价，计算合成标准不确定度及扩展不确定度。当大豆油质量分数为9.63%时，其扩展不确定度为0.10%(k=2)。当中链甘油三酸酯质量分数为10.00%时，其扩展不确定度为0.11%(k=2)。气相色谱法测定中、长链脂肪乳注射液中大豆油和中链甘油三酸酯含量的不确定度主要来源于对照品和样品溶液制备过程。该不确定度评定为实验过程的控制和测定结果的评估提供了参考，有利于保证该类药品的质量控制水平和检验结果的准确性。     

环保增塑剂柠檬酸三(2-乙基)己酯的合成

以柠檬酸和2-乙基己醇为原料,用结晶硫酸高铈为催化剂合成环保增塑剂柠檬酸三(2-乙基)己酯,考察了反应温度、催化剂用量、醇酸摩尔比、反应时间等因素对反应结果的影响,对合成的产品进行了红外光谱分析。实验结果表明,硫酸高铈催化合成柠檬酸三(2-乙基)己酯的最佳反应条件为n(2-乙基已醇)∶n(柠檬酸)=3.60∶1,催化剂用量为柠檬酸质量的1.5%,反应时间为90 m in,反应温度为150℃~160℃,在最佳反应条件下,柠檬酸三(2-乙基)己酯收率在98%以上。     

GC-MS/MS用于微波条件下PVC塑料中增塑剂向橄榄油迁移行为的研究

采用GC-MS/MS法研究了微波条件下PVC塑料中3种增塑剂(邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二(2-乙基)己酯(DEHP)和己二酸二(2-乙基)己酯(DEHA))在橄榄油中的迁移规律,考察了微波加热时间和微波功率对增塑剂迁移的影响,并与常规加热条件下的迁移进行比较。结果表明,3种增塑剂在橄榄油中的迁移量随微波功率和加热时间的增加而增大,且微波加热条件下的迁移量显著高于常规加热方式。     

模拟唾液浸泡塑料玩具溶出的邻苯二甲酸二(乙基己基)酯的固相微萃取-气相色谱法测定

利用新型溶胶 -凝胶富勒烯C60 涂渍的萃取头 ,采用顶空固相微萃取 -气相色谱法 ,研究了用模拟唾液浸泡塑料玩具溶出的邻苯二甲酸二(乙基己基)酯(DEHP)的固相微萃取(SPME)条件 ,并对聚氯乙烯玩具制品的模拟唾液浸泡液中增塑剂进行了分析和测定 ,方法的检出限为1.02μg/L ,实际样品的检出限为10.2×10-6(w) ,相对标准偏差RSD=10.5 %(n=7)。     

气相色谱-质谱法测定玩具中邻苯二甲酸酯类增塑剂

采用二氯甲烷作为萃取溶剂,超声提取塑料玩具和毛绒玩具中的6种增塑剂,提出了邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸(2-乙基己基)酯(DEHP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二正辛酯(DNOP)和邻苯二甲酸二异癸酯(DIDP)等6种增塑剂的气相色谱-质谱分析方法。在选定的试验条件下,BBP、DBP、DEHP和DNOP可以完全分离,通过比较保留时间、色谱图和峰面积(m/z 149),可实现以上4种物质的定性和定量分析。而DIDP和DINP的峰重叠,需通过选择m/z293,307质谱峰进行定量分析。结果表明方法能够有效地检测出玩具中邻苯二甲酸酯类增塑剂的含量。     

仿真饰品中邻苯二甲酸酯类增塑剂的含量测定和迁移风险考察

建立了仿真饰品中14种邻苯二甲酸酯类增塑剂的含量和迁移量测定的气相色谱-质谱(GC-MS)检测方法。考察了微波萃取、超声波萃取、快速溶剂萃取和索氏提取4种前处理方法对增塑剂含量测定的影响。在模拟人体温度及汗液环境下,考察了0～168 h内塑料仿真饰品中邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)和邻苯二甲酸二辛酯(DOP)3种增塑剂的迁移风险。结果表明微波萃取法的提取效率优于其余3种方法。所建立方法的定量限为5 mg/kg (邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)为25 mg/kg),在0.1～50 mg/L(DINP、DIDP在0.5～250 mg/L)范围内,线性相关系数在0.99以上,在3个添加水平下的回收率在90.95%与98.67%之间。在模拟条件下,DEHP的迁移风险较高,浸泡72 h后约有0.75%溶出,而DBP和DOP的溶出风险较低。该法的灵敏度高、回收率高、选择性好,能满足实际工作的要求。     

Determination of DEHP in blood products stored in plastic bags by HPLC

Summary High-performance liquid chromatography (HPLC) was used for the routine monitoring of the plasticizers di(2-ethylhexyl) phthalate (DEHP) and tri(2-ethylhexyl) trimellitate (TOTM), in blood products. It allows easy sample clean-up, solvent extraction using Celite 545 sorbent, good recoveries and opportunity to inject large number of samples without effect on column performance. The plasticizer levels were investigated in two types of poly(vinyl chloride) (PVC) bags containing whole blood plasma, platelet concentrates (PCs) during blood taking and storage.     

Evaporative loss kinetics of di(2-ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC

The migration of di(2-ethylhexyl)phthalate (DEHP) from poly(vinyl chloride) (PVC) to a surrounding gas phase at temperatures below 120 °C kinetically is controlled by evaporation. The effects on the DEHP loss rate of nitrogen flow rate, relative humidity and degradation of the plasticizer at 100 °C was assessed. The sample mass decreased linearly with time for both pristine DEHP and plasticized PVC at comparable rates, suggesting that a thin film of DEHP was present on the jacketing insulation during desorption. The latter hypothesis was supported by infrared spectroscopy and by the fact that DEHP is an amphiphilic molecule that will tend to aggregate at the surface with the hydrophobic 2-ethylhexyl units at the air interface. The effect on the migration rate of moisture present in the gas phase was negligible. The DEHP loss rate increased in a retarding non-linear fashion with increasing gas flow rate. In one of the experiments, DEHP was accidently degraded as revealed by discoloration, the presence of low molar mass degradation products (liquid chromatography) containing additional carbonyl groups (infrared spectroscopy) and an increase in the evaporation rate at temperatures between 100 and 130 °C.     

Kinetics of thermal degradation of poly(vinyl chloride)

Extensively studied thermal degradation of polyvinyl chloride (PVC) occurs with formation of free hydrogen chloride and conjugated double bonds absorbing light in visible region. Thermogravimetric monitoring of PVC blends degradation kinetics by the loss of HCl is often complicated by evaporation and degradation of plasticizers and additives. Spectroscopic PVC degradation kinetics monitoring by absorbance of forming conjugated polyenes is specific and should not be affected by plasticizers loss. The kinetics of isothermal degradation monitored by thermal gravimetric analysis in real time was compared with batch data obtained by UV/Visible absorption spectroscopy. Effects of plasticizer on kinetics of polyene formation were examined. Thermal degradation of PVC films plasticized with di-(2-ethylhexyl) phthalate (DEHP) and 1,2,4-benzenedicarboxylic acid, tri-(3-ethylhexyl) ester (TOTM) was monitored by conjugated double bonds light absorption at 350 nm at 160, 180, and 200 °C. Plasticizer-free PVC powder degradation kinetics and that of plasticized films were also obtained thermogravimetrically at temperatures ranging from 160 to 220 °C. Plasticizer-free PVC powder degradation and spectroscopically monitored degradation of plasticized PVC films occurred with the same apparent activation energy of ≈150 kJ mol⁻¹. No difference in degradation kinetics of films plasticized with DEHP and TOTM was detected.     

Human Metabolism of Bis(2-ethylhexyl)phthalate

Abstract

To study the human metabolism of bis (2-ethylhexyl)-phthalate (DEHP) urine samples were analyzed from non-uremic psoriatic patients, uremic patients undergoing hemodialysis treatments and patients undergoing cardiac bypass surgery using High Performance Liquid Chromatography (HPLC). The urine of dialyzed non-uremic patients contained phthalic acid, mono (2-ethylhexyl) phthalate and bis (2-ethylhexyl) phthalate. Other compounds identified were p-hydroxy benzoic acid, m-hydroxy benzoic acid, o-hydroxy hippuric acid, o-hydroxy benzoic acid and benzoic acid, which may be either diet dependent normal urinary constituents or metabolites of bis (2-ethylhexyl) phthalate. The levels of phthalic acid and bis (2-ethylhexyl) phthalate found in the urine of patients who were on total body oxygenators containing a membrane during cardiac bypass surgery were comparable to levels obtained from non-uremic psoriatic patients. Significant levels of phthalic acid were detected in the urine of the uremic patients studied while mono (2-ethylhexyl) phthalate and bis (2-ethylhexyl)-phthalate were present only in small amounts or were completely absent. In general, the urinary phthalate content of uremic patients increased with urinary volume.     

Tissue Bis(2-ethylhexyl)phthalate Levels in Uremic Subjects

Abstract

A method for the analysis of tissue DEHP levels was developed. Tissue homogenates were extracted with a chloroformrmethanol solution, followed by the addition of 1 g baked alumina to clean up the heavy matrices of the tissues. DEHP levels in tne tissues were determined by gas chromatography. Percent recovery of DEHP from the tissues ranged between 72.2 and 83.3%.

An experimentally produced acute renal failure in dogs (performing bilateral nephrectomy) was used for comparison of DEHP distribution in tissues from Control, Sham-Operated and Nephrectomized dogs. The highest concentration of DEKP was found in lung tissues of all three groups. DEHP levels in tissues of Nephrectomized dogs were significantly higher than those of Control and Sham-Operated dogs. With the exception of brain and liver, no significant difference in tissue DEHP levels were noted for Control and Sham-Operated dogs. Liver DEHP levels were 39.4 and 65.4 μg/g tissue for the Control and Sham-Operated dogs, respectively.

DEHP was found in various tissues of some, but not all of the subjects who received hemodialysis treatments, blood transfusions or blood which was previously in contact with PVC. No sufficient information is available at the present time to draw a relationship between exposure to DEHP and unchanged DEHP content in the tissues. However, DEHP does appear to accumulate in tissues and could be detected at death from some, but not all patients. It is more likely, however, that DEHP undergoes rapid metabolism in tissues.     

Molecularly imprinted microspheres and nanospheres for di(2-ethylhexyl)phthalate prepared by precipitation polymerization

Molecularly imprinted microspheres (MIMs, >3 μm) and nanospheres (MINs, ≈450 nm) for the environmental endocrine disruptor di(2-ethylhexyl)phthalate (DEHP) were prepared by a precipitation polymerization (PP) procedure. The effect of the dispersive solvents acetonitrile (ACN) and cyclohexane (CH), the cross-linkers ethylene glycol dimethacrylate (EDMA) and trimethylpropane trimethacrylate (TRIM), and the template on particle size and morphology of polymers was investigated in detail by scanning electron microscopy (SEM) and BET adsorption isotherm determination. When used as HPLC stationary phase, the microspheres exhibited strong affinity for the template DEHP with an imprint factor (IF) higher than 8.0 in ACN/water (60:40, v/v) as mobile phase. Furthermore, baseline separation of DEHP from benzyl butyl phthalate (BBP) and dibutyl phthalate (DBP) could be achieved. In contrast, no or only poor separation could be observed with non-imprinted polymeric polymers (NIPs) or imprinted bulk polymers (MIB), respectively. Similarly, the obtained MINs exhibited an imprinting effect in pure ACN, i.e. the bond amount of DEHP was significantly higher compared to NIPs, as was shown in rebinding experiments. Besides their use as an HPLC stationary phase, MIMs might further be applicable for SPE sample cleanup, while MINs could be used as a recognition layer on sensor surfaces. Figure Molecularly imprinting of di(2-ethylhexyl)phthalate (DEHP)     

Determination of Urinary Bis(2-ethylhexyl)phthalate Levels in Non-uremic Subjects by Gas Chromatography

Abstract

In vivo studies of urinary bis(2-ethylhexyl)phthalate (DEHP) levels in dogs and in non-uremic patients undergoing hemodialysis treatments for psoriasis were undertaken. Dogs were divided into 3 groups: Control, Sham-Operated, and Nephrectomized. Each dog received 225 mg DEHP per kilogram body weight via the femoral vein. Each of the non-uremic patients underwent hemodialysis therapy for 4–5 hours once a week for four consecutive weeks to treat their psoriatic condition. Specimens of 2 4 hr urine were collected and analyzed for DEHP by gas chromatography. The detection limit of DEHP in urine is 15 ng/ml. No detectable DEHP was found in the urine of all pre-injection specimens obtained from all three groups of dogs. The total urinary DEHP concentrations for the four day period were found to be 76.1 and 192.2 μg for the Control and the Sham-Operated dogs, respectively. No urine samples could be collected from the Nephrectomized dogs. DEHP levels were found in the 24 hr urine specimens from some of the non-uremic patients undergoing hemodialysis therapy. The DEHP concentrations ranged from non-detectable to 159.8 yg/24 hrs. Normal renal function seems to be necessary for the excretion of non-metabolized DEHP.     

Fast Chromatographic Separation of Plasticizers on Thin Layers of an Inorganic Ion-Exchanger: Quantitative Determination of Di(2-ethylhexyl)phthalate

Fast and selective separation of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di(2-ethylhexyl)phthalate (DEHP), benzyl butyl phthalate, diisodecyl phthalate, dimethyl adipate, diethyl adipate, di(2-ethylhexyl)adipate, triethyl citrate, tributyl citrate, tributyl acetyl citrate and n-butyl stearate have been developed on thin layers of inorganic ion-exchanger stannic silicate using a mixture of toluene + ethyl acetate (10:1, v/v) as mobile phase. The development distance and time were 12 cm and 25 min, respectively. Quantitative determination of DEHP was made at wavelength 280 nm by Camag TLC Scanner-3. Limit of quantitation for DEHP was 0.50 μg per zone while its limit of detection was 0.05 μg per zone.     

微溶剂萃取-气相色谱-质谱法测定水中邻苯二甲酸二(2-乙基己基)酯

取水样25mL,加入无水硫酸钠3.0g,加入环己烷2.0mL,振荡萃取3min。移取萃取了邻苯二甲酸二(2-乙基己基)酯(DEHP)的上层有机相2.0μL注入HP-5毛细管柱(30m×0.32mm,0.25μm)色谱分离后进行质谱测定。DEHP的质量浓度在50.0μg.L-1以内与其峰面积呈线性关系,方法的检出限(3S/N)为0.052μg.L-1。分析了早、中、晚不同时间的天津市自来水,并用标准加入法做回收试验,测得回收率在97.0%～109.4%之间,测定值的相对标准偏差(n=6)均小于2.5%。     

氧化石墨烯-邻苯二甲酸二(2-乙基己)酯表面分子印迹吸附剂的合成及应用

合成了以纳米材料氧化石墨烯为载体的表面分子印迹固相萃取材料，建立了分子印迹萃取联用高效液相色谱法检测牛奶塑料包装袋中的塑化剂邻苯二甲酸二（2-乙基己）酯（DEHP）残留的方法。以氧化石墨烯为基质、DEHP为模板分子、甲基丙烯酸为功能单体、N，N-二甲基甲酰胺为溶剂，通过沉淀聚合法合成表面分子印迹材料，优化了合成条件并对产品进行红外光谱、透射电镜表征。对产品的吸附性能（包括选择性、吸附平衡时间、吸附容量、重复使用率等）进行测定。在最优萃取条件下对牛奶包装袋提取液中DEHP进行选择性富集，通过高效液相色谱-紫外法检测，线性范围为0.5~50 mg/L，检出限为0.03 mg/L，定量限为0.1 mg/L。3种加标浓度下回收率为81.6%~92.4%，相对标准偏差（RSDs）小于7%。结果表明，该方法能够应用于实际样品中DEHP分析。