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1.
建立了高效液相色谱-串联质谱法测定土拉霉素在猪肝脏、肾脏、肌肉、皮脂和肺脏中的残留检测方法,并初步探讨了土拉霉素的基质效应.样品用乙腈提取,涡旋振荡离心后经正己烷脱脂,C18固相萃取柱净化后,40℃氮气吹干,用50%乙腈定容.以Penomenex Luna C18柱为色谱柱,乙腈-2 mmol,/L乙酸铵水溶液(含0....  相似文献   

2.
提出了固相萃取-超高液相色谱-串联质谱法同时测定植物油中百草枯和敌草快残留量的方法。取4.00 g样品,以10 mL正己烷为分散剂,涡旋1 min,加入20 mL体积比1∶1的0.1 mol·L^(-1)盐酸溶液-甲醇混合液,涡旋振荡提取20 min,离心5 min,弃去上层液体。取提取液15 mL经ProElut PXC固相萃取柱(用3 mL甲醇、3 mL水活化)净化,依次用3 mL水、3 mL甲醇淋洗,用3 mL体积比1∶1的2 mol·L^(-1)氯化铵溶液-甲醇混合液洗脱。流出液过0.22μm尼龙膜,滤液采用超高效液相色谱-串联质谱法测定其中百草枯和敌草快的含量。以Dikma HILIC色谱柱为固定相,以不同体积比的10 mmol·L^(-1)甲酸铵溶液(pH 3.0)-乙腈的混合液为流动相进行梯度洗脱,质谱分析采用多反应监测(MRM)模式,外标法定量。结果表明,百草枯和敌草快标准曲线的线性范围分别为2.0~200.0μg·L^(-1)、1.0~100.0μg·L^(-1),检出限(3S/N)分别为0.6,0.3μg·kg^(-1)。按照标准加入法进行回收试验,回收率为80.5%~93.6%,测定值的相对标准偏差(n=6)均小于10%。方法用于30个植物油样品分析,仅在3个样品中检出敌草快,检出量最高达10.5μg·kg^(-1)。  相似文献   

3.
以新型材料“对甲苯磺酸根-镁铝型水滑石”为分散固相萃取吸附剂,建立了一种同时测定谷物中麦草畏、草灭畏、草芽平和草芽畏4种苯甲酸类除草剂残留量的分散固相萃取-气相色谱法。谷物样品经10%丙酮水溶液涡旋提取、离心,用吸附剂分散固相萃取上清液,经离心、稀硫酸溶解吸附剂、乙醚-乙酸乙酯混合溶液萃取后以三甲基硅基重氮甲烷衍生化,采用气相色谱法测定4种苯甲酸类除草剂,以基质匹配校正曲线外标法定量。结果表明:谷物中4种苯甲酸类除草剂在10~200μg/kg添加水平范围内的平均回收率为84.8%~95.1%,相对标准偏差(RSD)为2.2%~7.2%,方法检出限(LOD)为1.33~3.09μg/kg,定量限(LOQ)为4.42~10.3μg/kg。  相似文献   

4.
建立了固相萃取法结合高效液相色谱同时检测焦糖色素中2-甲基咪唑(2-Methylimidazole,2-MEI)、4-甲基咪唑(4-Methylimidazole,4-MEI)和2-乙酰基-4-(1,2,3,4-四羟基丁基)咪唑(2-Acetyl-4-(1,2,3,4-tetrahydroxybutyl) imidazole,THI)的方法.样品经加水涡旋提取后,经混合型强阳离子交换固相萃取小柱富集净化,以乙腈-0.05%氨水(10∶90,V/V)为流动相,流速为0.6 mL/min,用反向色谱柱Polaris C18-A(250 mm×4.6 mm,5μm)柱分离,分别在二极管阵列检测器215 nm波长条件下检测焦糖色素中的2-甲基咪唑、4-甲基咪唑和287 nm波长条件下检测2-乙酰基4.(1,2,3,4-四羟基丁基)咪唑的含量.2-甲基咪唑、4-甲基咪唑和2-乙酰基-4-(1,2,3,4-四羟基丁基)咪唑在0.2~ 20 mg/L之间线性关系良好(r>0.9996),在10,25和100 mg/kg添加浓度的回收率范围为75.3% ~93.4%,相对标准偏差均小于10%,检出限分别为为2.6,3.0和1.5 mg/kg,定量限分别为8.5,10.0和5.0 mg/kg.  相似文献   

5.
建立了青葱、生姜、大蒜和辣椒酱中66种有机磷农药多残留的快速分析方法.样品用陶瓷均质子配合乙腈涡旋提取,盐析除水,提取液经Carb,C18和PSA粉末分散固相萃取净化后,采用超高效液相色谱-串联质谱(UPLC-MS/MS )进行分析,经HSS T3色谱柱分离,在电喷雾离子化正离子方式(ESI+)及多反应监测模式(MRM...  相似文献   

6.
提出了固相萃取-气相色谱-质谱法测定地下水中16种多环芳烃的方法。样品经ENVIC18固相萃取柱富集,依次用丙酮5 mL和二氯甲烷10 mL将16种多环芳烃从固相萃取柱上洗脱,用K-D浓缩器浓缩后,供气相色谱-质谱仪测定。纯水或自来水经固相萃取处理后,再用于配制标准溶液并绘制标准曲线。16种多环芳烃的检出限(3S/N)均小于2.0 ng.L-1。用该法分析地下水样品,所得结果的相对标准偏差(n=7)小于14.0%,加标回收率在84.3%~112.3%之间。  相似文献   

7.
Li4SiO4具有有利于离子传导的结构,为锂离子导体理想的基质材料[1].在硅酸盐体系中,硅的聚合态很复杂,难以得到纯相,鉴于固相法操作简单,在已有的文献中,合成方法多为固相法,但固相法不易保证成份的准确性、均匀性且合成温度较高.溶胶-凝胶法是近几年来发展起来的湿化学合成方法,用此法合成离子导体具有纯度高、均匀性好、颗粒小、反应过程易于控制等优点[2],而通常的溶胶-凝胶法是用金属醇盐与有机盐为前驱物,这样成本较高,且易造成污染.本文用金属醇盐及无机盐为前驱物,用溶胶-凝胶法合成了Li4SiO4纯相,并同一般固相法相比较,对合成的…  相似文献   

8.
潘小红  殷帅  刘玉玲  龙凌云  赵薇  孟庆玉 《色谱》2018,36(4):356-361
建立了全自动固相萃取-超高效液相色谱-串联质谱检测婴幼儿湿疹类产品中42种糖皮质激素的方法。样品用饱和氯化钠溶液分散后加乙腈涡旋提取,经亚铁氰化钾和醋酸锌沉淀大分子基质,然后用HLB固相萃取柱净化,待测液用Dikma EndeavorsilTM C18色谱柱(100 mm×2.1 mm,1.7 μm)分离,以0.1%(v/v)甲酸水溶液-乙腈为流动相进行梯度洗脱。在电喷雾正离子模式下以动态多反应监测方式测定,外标法定量。42种待测物在各自的范围内呈良好的线性关系,相关系数均大于0.998;在3个添加水平下,42种待测物的平均回收率为78.7%~101.5%,RSD为2.0%~8.8%(n=6);方法的检出限(LOD,S/N≥3)和定量限(LOQ,S/N≥10)分别为0.002~0.031 mg/kg和0.0007~0.103 mg/kg。该法简便快速,灵敏可靠,适用于婴幼儿湿疹类产品糖皮质激素的检测。  相似文献   

9.
《色谱》2016,(5)
建立了分散固相萃取-同位素稀释-高效液相色谱-串联质谱(dSPE-ID-HPLC-MS/MS)同时测定猪肉中26种β-受体激动剂残留的方法。样品经β-葡萄糖醛苷酶/芳基硫酸酯酶水解12 h后,用高氯酸沉淀蛋白质,取上清液,调节pH值为9,用乙腈涡旋提取,分散固相萃取净化。选用具有混合分离模式的新型色谱柱Poroshell 120Phenyl-Hexyl(100 mm×2.1 mm,4.0μm)对待测物进行分离,在电喷雾离子(ESI)源正离子模式下以多反应监测(MRM)模式采集数据并做定性筛查和定量分析。26种待测物在相应的浓度范围内线性关系良好,相关系数均大于0.99,在3个不同浓度的添加水平下,平均回收率为65.3%~108.5%,相对标准偏差(RSD)为2.7%~13.3%,检出限(LOD,S/N=3)和定量限(LOQ,S/N=10)分别为0.03~0.1μg/kg及0.1~1.0μg/kg。该方法成本低廉、灵敏可靠,适用于同时对猪肉产品中26种β-受体激动剂残留进行定性和定量筛查。  相似文献   

10.
适量水浸润的铁皮石斛样品经乙腈高速涡旋和超声提取。离心后,上清液采用分散固相萃取净化,吸附剂为C18和N-丙基乙二胺。采用分散固相萃取-气相色谱-串联质谱法测定净化液中41种农药的残留量。在气相色谱分离中采用Agilent VF-5MS色谱柱,在串联质谱分析中采用多反应监测模式。以外环氧七氯为内标,41种农药的检出限(3S/N)为0.001~0.024 mg·kg~(-1)。以空白样品为基体进行加标回收试验,所得回收率为75.1%~115%,测定值的相对标准偏差(n=6)为0.40%~11%。  相似文献   

11.
The reactions of [AuClL] with Ag(2)O, where L represents the heterofunctional ligands PPh(2)py and PPh(2)CH(2)CH(2)py, give the trigoldoxonium complexes [O(AuL)(3)]BF(4). Treatment of these compounds with thio- or selenourea affords the triply bridging sulfide or selenide derivatives [E(AuL)(3)]BF(4) (E=S, Se). These trinuclear species react with Ag(OTf) or [Cu(NCMe)(4)]PF(6) to give different results, depending on the phosphine and the metal. The reactions of [E(AuPPh(2)py)(3)]BF(4) with silver or copper salts give [E(AuPPh(2)py)(3)M](2+) (E=O, S, Se; M=Ag, Cu) clusters that are highly luminescent. The silver complexes consist of tetrahedral Au(3)Ag clusters further bonded to another unit through aurophilic interactions, whereas in the copper species two coordination isomers with different metallophilic interactions were found. The first is analogous to the silver complexes and in the second, two [S(AuPPh(2)py)(3)](+) units bridge two copper atoms through one pyridine group in each unit. The reactions of [E(AuPPh(2)CH(2)CH(2)py)(3)]BF(4) with silver and copper salts give complexes with [E(AuPPh(2)CH(2)CH(2)py)(3)M](2+) stoichiometry (E=O, S, Se; M=Ag, Cu) with the metal bonded to the three nitrogen atoms in the absence of AuM interactions. The luminescence of these clusters has been studied by varying the chalcogenide, the heterofunctional ligand, and the metal.  相似文献   

12.
The equilibrium swelling study of polyurethanes (PU) was carried out in various solvents in order to calculate their solubility parameter. The kinetics of swelling and sorption have also been studied in 1,4‐dioxane at 30°C. The PU was synthesized by reacting a novel polyol (castor oil derivative and epoxy based resin, EpxR) and one of the polyethylene glycols (PEG 200, PEG 400, PEG 600) with different weight compositions, with a toluene diisocyanate (TDI) adduct (derived from toluene diisocyanate and R60 polyol). Different NCO/OH ratio viz. 1, 1.3 and 1.7 were employed in the study. The results were found to vary with the weight composition of polyol components, as well as the crosslink density of the samples. The sorption behavior is also found to vary with the molecular weight of polyethylene glycol employed in the preparations of the polyurethanes. Kinetic studies of swelling revealed that the sorption is anomalous in nature. The diffusion coefficient (D) increased with an increase in the NCO/OH ratio and decreased with an increase in chain length of polyethylene glycol. The sorption coefficient (S) decreased with an increase in crosslink density (NCO/OH) and increased with increasing polyethylene glycol (i.e., PEG 200, PEG 400, and PEG 600) moieties in the polyurethanes. The molecular weight between two crosslink points was calculated using the Flory Rehner equation (24), and hence, the number of chains per unit volume (N) and degree of crosslinking (ν) in all the samples were determined.  相似文献   

13.
The reduction of ammonium pertechnetate with bis(diphenylphosphino)methane (dppm), and with diphenyl-2-pyridyl phosphine (Ph(2)Ppy), has been investigated. The neutral Tc(II) complex, trans-TcCl(2)(dppm)(2) (1), has been isolated from the reaction of (NH(4))[TcO(4)] with excess dppm in refluxing EtOH/HCl. Chemical oxidation with ferricinium hexafluorophosphate results in formation of the cationic Tc(III) analogue, trans-[TcCl(2)(dppm)(2)](PF(6)) (2). The dppm ligands adopt the chelating bonding mode in both complexes, resulting in strained four member metallocycles. With excess PhPpy, the reduction of (NH(4))[TcO(4)] in refluxing EtOH/HCl yields a complex with one chelating Ph(2)Ppy ligand and one unidentate Ph(2)Ppy ligand, mer-TcCl(3)(Ph(2)Ppy-P,N)(Ph(2)Ppy-P) (3). The cationic Tc(III) complexes, trans-[TcCl(2)(Ph(2)P(O)py-N,O)(2)](PF(6)) (4) and trans-[TcCl(2)(dppmO-P,O)(2)](PF(6)) (5) (Ph(2)P(O)py = diphenyl-2-pyridyl phosphine monoxide and dppmO = bis(diphenylphosphino)methane monoxide), have been isolated as byproducts from the reactions of (NH(4))[TcO(4)] with the corresponding phosphine. The products have been characterized in the solid state and in solution via a combination of single-crystal X-ray crystallography and spectroscopic techniques. The solution state spectroscopic results are consistent with the retention of the bonding modes revealed in the crystal structures.  相似文献   

14.
Effect of nitrogen and argon matrices on the C-H asymmetric stretching and bending infrared frequencies of the acetylene molecule, C(2)H(2), has been studied by matrix isolation experiments as well as by calculations at MP2 level of theory. The complexes of C(2)H(2) in nitrogen and argon matrices, viz., C(2)H(2)(N(2))(m) (with m=2-8) and C(2)H(2)(Ar)(n) (with n=2-10) are theoretically explored. The computed acetylenic C-H asymmetric stretch in C(2)H(2)-nitrogen complexes shows a redshift of 3.0 to 11.9 cm(-1) compared with the frequencies of the free acetylene molecule, and a corresponding blueshift of 7.4 to 26.2 cm(-1) when C(2)H(2) is complexed with argon atoms. The trends in the computed shifts are in good agreement with the experiments. The molecular electrostatic potential minimum of C(2)H(2) becomes more negative when complexed with nitrogen than on complexation with argon. This observation implies a greater basic character for C(2)H(2) in the nitrogen matrix, favoring the formation of H-pi(C(2)H(2)-MeOH) complex as compared to that in the Ar matrix. Experimentally the preferential formation of H-pi(C(2)H(2)-MeOH) complex in the N(2) matrix has indeed been observed.  相似文献   

15.
The effect of native cyclodextrins (alpha, beta, or gammaCD with six, seven and eight glucose units, respectively), hydroxypropyl-beta-cyclodextrin (HPCD), chitosan (CHT) and glucose in water solution or water with n-propylamine (PA) as co-solvent upon the UV-vis and fluorescence properties of poorly fluorescent N-methyl carbamates pesticides (C) as bendiocarb (2,2-dimethyl-1,3-benzodioxol-4-ol methylcarbamate, BC) and promecarb (3-methyl-5-(1-methylethyl)phenol methylcarbame, PC) was examined. Fluorescent enhancement was found for both substrates with all CDs in water or PA-water except from PC with alphaCD. The addition of CHT increases the fluorescence of BC but decreases the fluorescence of PC, and glucose addition gives in both cases no spectral changes. Host-guest interaction was clearly determined by fluorescence enhancement with betaCD and HPCD with a 1:1 stoichiometry for the complexes (C:CD). The values obtained for the association constants (K(A), M(-1)) were (6+/-2)x10(2) and (2.3+/-0.3)x10(2) for BC:betaCD and BC:HPCD complexes, respectively. For PC:betaCD and PC:HPCD the values of K(A) were (19+/-2)x10(2) and (21+/-2)x10(2), respectively. The ratio of the fluorescence quantum yields for the bound and free substrates (phi(CCD)/phi(C)) was in the range 1.74-3.8. The limits of detection (L(D), microg mL(-1)) for the best conditions were (0.57+/-0.02) for BC with HPCD and (0.091+/-0.002) for PC with betaCD in water. Application to the analysis in pesticide spiked samples of tap water and fruit yields satisfactory apparent recoveries (84-114%), and for the extraction procedure in fruits and a commercial formulation, recoveries were of 81-98% and 104%, respectively. The method is rapid, simple, direct, sensitive and useful for pesticide analysis.  相似文献   

16.
The aim was to investigate the relationship between the bond length and the electron density at the bond critical point in homonuclear X--X and Z--Z and heteronuclear C--Z bonds (X = Li-F, Z = Na-Cl). The d,rho(c) pairs were obtained from 472 target bonds in DFT-optimized (B3LYP/6-311+G(d,p)) small molecular species. These species were selected arbitrarily but with a view to maximize the range widths WR for each atom combination. It was found that (i) with one clear exception, the d(A - A) means (A = X or Z) correlate linearly with the bond lengths d(A(2)) of the respective diatomic molecules; (ii) the d(A - A) means correlate parabolically with n, the formal number of valence electrons in the atoms of the bond; and (iii) with increasing sample size N the ratio WR(rho(c))/WR(d) appears to converge toward a representation f [WR(rho(c))/WR(d)](N-->infinity) characteristic of A. Detailed analysis of the d,rho(c) relationship has shown that by and large simple power regression accounts best for the DFT data. The regression coefficients of d = arho(c) (-b) and rho(c) = alphad(-beta) (b, beta > 0) vary with n in a seemingly irregular manner but one that is consistent with simple chemical notions. The d(A(2)) can be approximated in terms of multilinear MO electron occupancies.  相似文献   

17.
A simple, economic and sensitive method for selective determination of As(III) and As(V) in water samples is described. The method is based on selective coprecipitation of As(III) with Ce(IV) hydroxide in presence of an ammonia/ammonium buffer at pH 9. The coprecipitant was collected on a 0.45 µm membrane filter, dissolved with 0.5 mL of conc. nitric acid and the solution was completed to 2 or 5 mL with distilled water. As(III) in the final solutions was determined by graphite furnace atomic absorption spectrometry (GFAAS). Under the working condition, As(V) was not coprecipitated. Total inorganic arsenic was determined after the reduction of As(V) to As(III) with NaI. The concentration of As(V) was calculated by the difference of the concentrations obtained by the above determinations. Both the determination of arsenic with GF-AAS in presence of cerium and the coprecipitation of arsenic with Ce(IV) hydroxide were optimised. The suitability of the method for determining inorganic arsenic species was checked by analysis of water samples spiked with 4–20 µg L?1 each of As(III) and As(V). The preconcentration factor was found to be 75 with quantitative recovery (≥95%). The accuracy of the present method was controlled with a reference method based on TXRF. The relative error was under 5%. The relative standard deviations for the replicate analysis ( n?=?5) ranged from 4.3 to 8.0% for both As(III) and As(V) in the water samples. The limit of detection (3σ) for both As (III) and As(V) were 0.05 µg L?1. The proposed method produced satisfactory results for the analysis of inorganic arsenic species in drinking water, wastewater and hot spring water samples.  相似文献   

18.
Synthesis of graft copolymers with polyisobutylene branch chains   总被引:1,自引:0,他引:1  
吴一弦 《高分子科学》2010,28(3):449-456
<正>The copolymerization of 4-vinylbenzyl chloride(VBC) and vinyl acetate(VAC) was carried out in toluene at 75℃via radical polymerization using 2,2'-azo-bis-(isobutyronitrile)(AIBN) as an initiator.The random copolymers of poly(4-vinylbenzyl chloride-co-vinyl acetate)(P(VBC-co-VAC)) with number average molecular weight(M_n) from 2000 to 6900,relatively narrow molecular weight distribution(MWD,M_w/M_n ca.2.0) and with different copolymer composition of 4-vinylbenzyl chloride(VBC) from 17 mol%to 62 mol%could be obtained.The P(VBC-co-VAC) copolymers with an average number of 7 to 13 initiating sites of benzyl chloride per macromolecule could be used for the cationic polymerization of isobutylene(IB).The cationic polymerizations of IB were further conducted by using P(VBC-co-VAC) copolymers as macroinitiators in conjunction with TiCl_4 at -40℃in CH_2Cl_2.The effects of VBC/TiCl_4(molar ratio) on monomer conversion,M_n and MWD of the resultant copolymers were investigated under 3 sets of conditions.It is found that P(VBC-co-VAC)-g-PIB copolymers with relatively narrow MWD(M_w/M_n ca.2.0) and with terminal tert-chlorine functional groups in branched PIB chains could be successfully synthesized when VBC/TiCl_4(molar ratio) was set in the range from 0.10 to 1.12.The unimodal GPC curve of the P(VBC-co-VAC)-g-PIB copolymers by RI detector was almost in harmony with the GPC curve by UV detector.The TEM image of the P(VBC-co-VAC)-g-PIB copolymer stained by RuO indicated that the copolymer formed a two-phase morphology with P(VBC-co-VAC)-rich domains of 20-100 nm in size tethered by PIB branch segments.  相似文献   

19.
The 1:1 molecular complex between oxetane and water has been investigated by using free-jet millimeter-wave spectroscopy. The rotational spectra of five isotopomers (with H(2)O, D(2)O, DOH, HOD and H(2) (18)O) have been assigned. Partial r(0) and r(s) structures of the complex have been derived. The water moiety lies in the plane of symmetry of oxetane, with the "free" hydrogen E with respect to the ring. The oxetane ring appears to be slightly nonplanar, with the C(beta) carbon tilted on the opposite side of the water unity. The three atoms involved in the hydrogen bond adopt a linear arrangement with an O(ring).H distance of about 1.86 A, and the angle between the COC bisector and the O(ring).H bond being congruent with 106 degrees. Additionally, quantum-chemical calculations for the complex were performed and were found to be in agreement with the experimental results.  相似文献   

20.
The structural and electronic properties of Ce(1-x)Cu(x)O(2) nano systems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Cu atoms embedded in ceria had an oxidation state higher than those of the cations in Cu(2)O or CuO. The lattice of the Ce(1)(-x)Cu(x)O(2) systems still adopted a fluorite-type structure, but it was highly distorted with multiple cation-oxygen distances with respect to the single cation-oxygen bond distance seen in pure ceria. The doping of CeO(2) with copper introduced a large strain into the oxide lattice and favored the formation of O vacancies, leading to a Ce(1-x)Cu(x)O(2-y) stoichiometry for our materials. Cu approached the planar geometry characteristic of Cu(II) oxides, but with a strongly perturbed local order. The chemical activities of the Ce(1-x)Cu(x)O(2) nanoparticles were tested using the reactions with H(2) and O(2) as probes. During the reduction in hydrogen, an induction time was observed and became shorter after raising the reaction temperature. The fraction of copper that could be reduced in the Ce(1-x)Cu(x)O(2) oxides also depended strongly on the reaction temperature. A comparison with data for the reduction of pure copper oxides indicated that the copper embedded in ceria was much more difficult to reduce. The reduction of the Ce(1-x)Cu(x)O(2) nanoparticles was rather reversible, without the generation of a significant amount of CuO or Cu(2)O phases during reoxidation. This reversible process demonstrates the unusual structural and chemical properties of the Cu-doped ceria materials.  相似文献   

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