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1.
以过氧化苯甲酰(BOP)为模板分子,甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用热聚合法在多壁碳纳米管(MWNTs)表面制备印迹聚合物(MWNTs-MIPs)。采用红外和热重分析等技术对聚合物结构进行表征。采用液相色谱考察该分子印迹聚合物对过氧化苯甲酰的吸附特性。结果表明该印迹聚合物对过氧化苯甲酰表现出特异性吸附,该印迹聚合物对模板分子存在一种结合位点,其最大表观结合量为56.20 µmol/g。该印迹聚合物成功应用于固相萃取富集面粉中微量过氧化苯甲酰,浓度富集因子为526。  相似文献   

2.
A series of experiments were conducted to investigate elements which affect the enantiomeric recognition properties of molecularly imprinted polymers (MIPs) in the HPLC mode. Our results show that the recognition properties of MIPs are greatly influenced by the mobile phase used. For a polymer prepared in acetonitrile, a good enantiomeric separation was observed when acetonitrile-based mobile phase was used, when the mobile phase was changed to chloroform-based, no enantiomeric recognition was observed although the sample molecule was retarded. This indicates that the specific co-operative binding interactions between the functional groups at the imprinted polymer's recognition sites and the sample molecule were considerably disrupted and only non-specific interactions remained. When the mobile phase was changed back to acetonitrile-based, the recognition was regained. In contrast, for polymers prepared in chloroform, chloroform-based mobile phase gave much better separation than acetonitrile-based mobile phase. When other solvents were tested, significant solvent effects were generally observed. Based on these observations, the recognition properties of the methacrylic acid (MAA)-co-ethylene glycol dimethacrylate (EGDMA) polymers were reinvestigated, and the results show that by simply using an optimised mobile phase system, significantly improved recognition over previously reported results was observed. For a polymer made against Cbz-L-Trp, 100 microg of Cbz-D,L-Trp was separated with a separation factor (alpha) of 4.23 and a resolution (Rs) of 3.87, whereas in the previous report, 10 microg of Cbz-D,L-Trp was only separated with alpha = 1.67 and Rs = 0.1. It is generally realised that the imprinted polymer's recognition property is also very much influenced by the nature of the polymer network. It was shown that the recognition decreased with a decrease in the apparent degree of cross-linking (molar percentage of cross-linker in the polymerisation mixture). Nonetheless, our results show that in our optimised assay system a significant separation could still be obtained on a polymer which was only 22% cross-linked. We consider this to be of importance, since it may suggest a way of imprinting larger molecules because of the possibly improved mass transfer in low cross-linking density polymers. It was reported that when trifunctional cross-linkers [for example: trimethylolpropane trimethacrylate (TRIM)] were used as the cross-linker instead of EGDMA, considerably improved enantiomeric separation and resolving capability were observed. Our results show that the improved performance of the MAA-co-EGDMA MIPs is actually comparable to the performance of the MIPs prepared with those trifunctional cross-linkers. The combination of a hydrogen bonding functional monomer (acrylamide) with TRIM also did not give improved recognition. The results suggest that although the three-dimensional network of these two kinds of polymer may be quite different, the observed recognition improvements were probably largely due to solvent effect.  相似文献   

3.
The use of molecularly imprinted polymers (MIPs) prepared by ring-opening metathesis polymerization (ROMP) for bisphenol A (BPA) was reported in this article. The resulting MIPs have high imprinting and adsorption capacities, and can be used for separation and determination of BPA in environmental water samples. The successful application of ROMP in the molecular imprinting field is described here. For the first time, two cross-linkers (dicyclopentadiene and 2,5-norbornadiene) and two Grubbs catalysts (first and second generation) were investigated to compare their effects on the binding performance of MIPs. The ROMP technique is able to create the imprinted polymers within 1 h under mild conditions. Furthermore, it can provide MIPs with obvious imprinting effects towards the template, very fast template rebinding kinetics, high binding capacity and appreciable selectivity over structurally related compounds. The adsorption process for MIPs in this study can be completed within 45 min, which is much faster than that of bulk MIPs synthesized by traditional free-radical polymerization. The resulting imprinting polymer was evaluated for its use as a sorbent support in an off-line solid-phase extraction approach to recover BPA from diluted aqueous samples. The optimized extraction protocol resulted in a reliable MISPE method suitable for selective extraction and preconcentration of BPA from tap water, human urine and liquid milk samples. This article demonstrates the practical feasibility of the MIPs prepared via ROMP as solid-phase extraction materials.  相似文献   

4.
This study concentrates on the production of covalent molecular imprint polymers (MIPs) as highly selective sorbents for nortriptyline (NOR), a representative tricyclic antidepressant (TCA). The functionalized template contains a polymerizable 4-vinylphenyl carbamate moiety used to bind the template molecule to the polymer matrix. Polymerization with a cross-linker followed by hydrolytic cleavage of the labile carbamate functionality leaves an MIP with selective binding sites capable of binding template through hydrogen bonding interactions. Demonstrated chromatographically through a "selection index", these MIPs showed high selectivity for the template molecule (NOR) among a library of structurally similar compounds. The recognition was found to correlate with structural similarity to the template compound. A direct comparison between covalent and non-covalent molecular imprinting strategies reveals a great deal of improvement in the peak shape of the retained compound resulting from covalent imprinting (evidenced by peak asymmetry factors A.).  相似文献   

5.
In this research, molecular imprinting polymers (MIPs) for D-arabinitol were synthesized using a bulk polymerization method through a noncovalent approach. The MIPs were prepared by using D-arabinitol as a template, acrylamide as a functional monomer, ethylene glycol dimethacrylateas cross-linker, benzoyl peroxide as an initiator and dimethyl sulfoxideas a porogen. MIPS was synthesized in several formulas with a different molar ratio of template to functional monomers and cross-linker. Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) were used to characterize the MIPs produced. A batch rebinding assay was used to test the binding efficiency of each formula. Batch rebinding test results revealed that MIPsF3 with a molar ratio of the template: monomer and crosslinker ratio respectively (1: 4: 25) had the highest binding capacity at 1.56 mgg -1 . The results of isotherm adsorption showed that the MIPs produced followed the Freundlich equation with an R-value of 0.97. The MIPs produced was also selective toward its isomeric compounds (i.e. L-arabinitol, adonitol, xylitol, and glucose). The extraction efficiency of the MIPs against D-arabinitol was 88.98%.  相似文献   

6.
以泰乐菌素为虚拟模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了对替米考星具有高选择性的分子印迹聚合物。考察了二甲基甲酰胺、甲醇、丙酮和氯仿4种致孔剂对合成聚合物性能的影响。通过正交实验优化的聚合配方为:1.0mmol泰乐菌素,8.0mmol甲基丙烯酸,20.0mmol乙二醇二甲基丙烯酸酯,6.0mL氯仿,20.0mg偶氮二异丁腈。研究了将该聚合物作为固相萃取填料分离、富集替米考星的萃取条件和萃取性能。当萃取柱依次用甲醇和水(pH9.0)活化,乙腈溶液上样,甲醇和氯仿分别洗涤,3mL氨化甲醇(95:5,V/V)洗脱时,替米考星在分子印迹固相萃取柱上的回收率达到90%以上,而非分子印迹固相萃取柱的回收率仅为32%。  相似文献   

7.
For preparing the phenobarbital(PHN) molecularly imprinted polymers(MIPs) with higher adsorption and selectivity properties, we used the M062 X/6-31 g(d,p) method of density functional theory to predict the various properties of PHN-MIPs. Here PHN is as the imprinted molecule and acrylamide(AM) as the functional monomer. The ethylene glycol dimethacrylate,trimethylolpropane trimethacrylate, divinyl benzene, and pentaerythritol trimethacrylate are as the cross-linking agents, respectively. The acetonitrile, chloroform, toluene, and tetrahydrofuran are used as the solvents, respectively. The configurations of the molecular imprinting self-assembly system for PHN and AM have been simulated to study their bonding sites, binding energy, amount of hydrogen bond, and interaction mechanism. The essence of imprinting interaction for PHN and AM has been revealed by the atomic in the molecule theory. Meanwhile, the analogues of PHN were used to discuss the selectivity property of the stable PHN-AM complex. The results show that the PHN interacts with AM through hydrogen bonds. When the imprinting molar ratio of PHN-AM is1:6 and the THF is as the solvent, the amount of their hydrogen bonds is the most, the binding energy is the lowest, and their configuration is the most stable. In comparison with the other cross-linking agents(EGDMA, TRIM, and DVB), the PETA is more suitable for PHN-MIPs. The selective property of PHN-MIP to PHN is excellent when PHN and DMBA exist at the same time.  相似文献   

8.
魏琴  陈秀秀  白丽红  赵亮  黄艳萍  刘照胜 《色谱》2021,39(11):1171-1181
液晶分子印迹聚合物(MIPs)因刚性液晶单体的加入而在超低交联度水平下也能印迹和识别模板分子,有效解决了传统MIPs因高交联度造成的位点包埋、结合容量低、传质慢等问题。尽管液晶MIPs具有如此独特的优势,但却面临着由于交联度的大幅度降低而导致印迹效果下降的问题。为了研究液晶MIPs的结合特性,制备具有良好印迹效果的低交联液晶MIPs,该文通过二次接枝聚合,制备了一系列不同交联度的液晶分子印迹整体柱,用高效液相色谱法研究了聚合参数与印迹整体柱亲和性的关系。实验中选用三羟甲基丙烷三甲基丙烯酸酯(TRIM)为交联剂,以甲苯和十二醇为致孔剂合成整体柱骨架,并在此基础上以(S)-萘普生为模板,加入液晶单体4-氰基苯基单环己基乙烯(CPCE)进行二次聚合接枝。实验中系统考察了流动相中乙腈比例及缓冲液pH值对色谱保留的影响,结果发现液晶单体的加入使得MIPs对萘普生保留控制机制由原来的氢键作用变为了疏水作用;通过动态吸附实验得到的突破曲线经前沿分析及对吸附等温线Langmuir、Freundlich和Scatchard分析拟合,发现交联度为15%时液晶MIPs印迹因子最大(3.78)、非均一性最强,且特异性吸附量高于非特异性吸附量。液晶MIPs的计量置换模型(SDM-R)分析表明,液晶印迹整体柱对模板分子的总亲和力(ln A=0.645)明显高于其类似物;而从空间匹配程度看,与液晶印迹整体柱空间匹配程度最高的是酮洛芬而非模板分子,但液晶印迹整体柱对酮洛芬的总亲和力(ln A=0.242)不及模板分子的一半,表明在本低交联液晶印迹系统中,空间效应不是决定印迹系统识别能力的主要因素。进一步的分离热力学研究发现,低交联液晶印迹柱的|ΔΔH|<T|ΔΔS|,而交联度为70%的非液晶MIPs柱的|ΔΔH|>T|ΔΔS|,表明液晶MIPs的分离过程是一个熵控制过程,而常规无液晶MIPs的分离过程是一个焓控制过程。上述结果表明,液晶单体的加入改变了MIPs的识别机制,适当的低交联度可显著提高液晶MIPs的识别性能,因此液晶MIPs这些特质有望使其成为新一代的MIPs。  相似文献   

9.
采用DFT/B3LYP-D3(BJ)/6-31G(d,p)计算模拟方法分析探讨了双(对硝基苯基)磷酸酯(BNPP)替代对氧磷(PO)用作有机磷神经毒剂分子印迹聚合物(MIPs)模板分子模拟物的可行性. 通过对比BNPP和PO两种模板分子分别与各种功能单体形成的复合物的构型稳定性和结合能大小, 确认了以4-甲基丙烯酰胺基安替比林(MAAP)为第一功能单体、 甲基丙烯酸(MAA)为第二功能单体组成的双功能单体体系是最佳功能单体体系. 以BNPP为模板分子、 MAAP-MAA为单体体系、 乙二醇二甲基丙烯酸酯(EGDMA)为交联剂、 纳米二氧化硅为载体, 采用表面印迹技术制备了SiO2@BNPP分子印迹聚合物, 并对聚合物的表面形貌和吸附性能进行了分析. 实验结果表明, 当n(BNPP)/n(MAAP)/n(MAA)/n(EGDMA)为1∶1∶4∶20时, MIPs的吸附容量最大可达19.03 mg/g, 对4-硝基苯酚(4-NP)的分离因子为17.50; MIPs能够快速吸附模板分子, 5 min即可达到吸附平衡量的92%, 动态吸附平衡时间仅为15 min, 重复使用5次后仍能保持良好的吸附能力; 吸附过程符合准二级动力学模型和Langmuir等温吸附模型, Scatchard方程分析表明MIPs中存在两类吸附作用位点. 实验结果与计算模拟结果的一致性表明, 计算模拟对有机磷神经毒剂MIPs的设计和研究具有一定的指导意义.  相似文献   

10.
Analysis of recognition of fructose by imprinted polymers   总被引:1,自引:0,他引:1  
Binding of fructose to the fructose imprinted polymer (MIP(Frc)) and pinacol imprinted polymer (control) were studied both in batch and a flow through mode. The influence of the cross-linkers ethylene glycol dimethacrylate (EDMA) and trimethylolpropane trimethacrylate (TRIM) on the binding characteristics was analysed. TRIM cross-linked MIPs showed a lower (unspecific) binding for the control polymer (pinacol imprinted) and higher binding of fructose as compared with the EDMA-MIPs. Furthermore interactions of a TRIM cross-linked molecularly imprinted polymer against fructose and its corresponding template were studied using a thermistor. Label-free detection of fructose was realised in the range of 0.5-10mM. The difference in enthalpy changes between specific binding of fructose to boronic acid moieties of the MIP and non-specific binding to the matrix leads to an 18-fold higher apparent imprinting factor than batch binding studies. Cross-reactivity studies using MIP sensor indicate that the interaction of fructose to MIP generates higher signal than disaccharides. The studies described in this paper demonstrate the potential of direct characterisation of molecular binding events.  相似文献   

11.
酚酞分子印迹聚合物的制备及特异吸附性能   总被引:1,自引:0,他引:1  
石慧丽  樊静  魏娅方 《应用化学》2009,26(8):971-975
以泻药酚酞为模板分子,4-乙烯基吡啶为功能单体制备了模板分子和功能单体不同比例的一系列酚酞分子印迹聚合物。利用扫描电镜对聚合物进行了表面形态分析,采用静态平衡实验法研究了聚合物对模板分子及其类似物的吸附行为和选择性识别能力。实验结果表明,所制备的分子印迹聚合物,吸附 3 h 后基本接近最大吸附量,其中模板分子、4-乙烯基吡啶和交联剂的摩尔比为 1∶6∶20的MIP2的印迹因子为 2.30,效果最佳。Scatchard 分析表明, 在所研究的浓度范围内,吸附过程存在两类结合位点,一类高亲和力结合位点的离解常数为Kd1= 0.63 mmol/L,最大表观结合量 Qmax1 = 25.4 umol/g,另一类低亲和力结合位点的离解常数为 Kd2 =3.5 mmol/L,最大表观结合量 Qmax2 = 61.9 umol/g,通过与酚酞类似物质在酚酞分子印迹聚合物上的吸附行为比较,表明对酚酞具有很好的选择性吸附。  相似文献   

12.
《高分子科学》2019,37(12):1305-1318
Computational strategies have been employed to investigate the influence of the nature of monomers and cross-linker in order to design three dimensional imprinted polymers with selective recognition sites for L-phenylalanine benzyl ester(L-PABE) molecule.Here, computational chemistry methods were applied to screen the molar quantity of functional monomers that interact with one mole of the template molecule. Effects of the nature of functional monomer, cross-linker, and molar ratio were determined computationally using density functional calculations with B3LYP functional and generic 6-31G basis set. Methacrylic acid(MAA) and ethylene glycol dimethacrylate(EGDMA) were used as the functional monomer and crosslinking agent, respectively. L-PABE imprinted polymer layered on multiwalled carbon nanotube(MWCNT) and conventional bulk MIP were synthesised and characterized as well. To investigate the influence of pre-organization of binding sites on the selectivity of L-PABE, respective non-imprinted polymers were also synthesised.MWCNT-MIPs and MIPs exhibited the highest adsorption capacity towards L-PABE. The synthesized polymers revealed characteristic adsorption features and selectivity towards L-PABE in comparison with those of its enantiomer analogues.  相似文献   

13.
Molecular simulations are widely used to model molecularly imprinted polymers(MIPs) in order to enhance their adsorption and selectivity. In this study, chloramphenicol(CAP) and acrylamide(AM) were used as the template and functional monomer, respectively, and pentaerythritol triacrylate(PETA), ethylene glycol dimethacrylate (EGDMA), and trimethylolpropane trimethylacrylate(TRIM) were used as cross-linking agents. The ωB97XD/6-31G(d,p) density functional theory method was employed to simulate binding sites, binding energy, the number of hydrogen bonds, the imprinted molar ratio, which produced the most stable complex, and the interaction mechanism. The cross-linking agent was optimized based on the binding energy. The atoms in molecules theory were used to study the nature of the imprinting effects. The theoretical calculations revealed that CAP and AM formed ordered complexes via hydrogen bonding interactions when the molar ratio between CAP and AM was 1:7 using TRIM as the cross-linking agent. The CAP-AM complex(molar ratio 1:7) had the most stable structure, the largest number of hydrogen bonds, and the smallest ∆E. The experimental results indicate that the CAP-MIPs formed perfect microspheres with an average particle size of 314 nm. Scatchard plot analysis showed that the CAP-MIPs had only one type of binding site over the studied concentration ranges. The dissociation equilibrium constant and maximum apparent adsorption capacities were 1887.35 mg/L(5.84 mmol/L) and 155.56 mg/g(0.482 mmol/g), respectively.  相似文献   

14.
Ibuprofen and ketoprofen are chemically similar non‐steroidal anti‐inflammatory drugs widely used in the treatment of arthritis. Using a molecular imprinting technique, a simple and rapid method was developed for the simultaneous separation and determination of ibuprofen and ketoprofen. Molecular imprinting introduces artificial binding sites into a synthetic polymer matrix, allowing it to exhibit selective rebinding of template molecules. Imprinted polymers can be regarded as an HPLC stationary phase, important for pharmaceutical analysis. Most molecularly imprinted polymers (MIPs) are synthesized by free radical polymerization of functional monomers, resulting in an excess of crosslinking monomers. In this study, MIPs have been prepared with a ibuprofen template, which can form intramolecular hydrogen bonds. Methacrylic acid (MAA) and ethyleneglycol dimethacrylate (EGDMA) were used as the functional monomer and cross‐linker, respectively. Bulk polymerization was carried out at 4 °C under UV radiation. The resulting MIP was ground into 25?44 μm particles, which were slurry‐packed into analytical columns. Template molecules were removed by methanol‐acetic acid (9:1, v/v). We evaluated the template binding performance of the MIP using HPLC, with ultraviolet (UV) detection at 234 nm. Chromatographic resolution of ibuprofen and ketoprofen on the MIPs were appraised using buffer/acetonitrile (45/55, v/v) as the mobile phase. Results show that the MIPs prepared using ibuprofen as the template had a significant molecular imprinting effect. The method was successfully applied to the separation and analysis of ibuprofen and ketoprofen in pharmaceuticals.  相似文献   

15.
In this paper, we describe the synthesis and evaluation of molecularly imprinted polymers (MIPs), prepared using 2′,3′,5′-tri-O-acyluridines as ‘dummy’ templates, for the selective recognition of uridine nucleosides. The MIPs were synthesised using a non-covalent approach with 2,6-bis-acrylamidopyridine (BAAPy) acting as the binding monomer and ethylene glycol dimethacrylate (EGDMA) as the cross-linking agent. The MIPs were evaluated in terms of capacity, selectivity and specificity by analytical and frontal liquid chromatography measurements. The results obtained in organic mobile phases suggest that the nucleosides are specifically bound to the polymer by the complementary hydrogen bonding motifs of the binding monomer and the nucleoside bases. The MIPs exhibited relatively high imprinting factors for 2′,3′,5′-tri-O-acyluridines, while they did not show any binding capacity for other nucleosides lacking the imide moiety on their base. Moreover, the presence of ester-COO groups in the EGDMA cross-linker may lead to the formation of additional hydrogen bonds with the 2′,3′ and/or 5′-OH of sugar part, allowing enhancement of the recognition of the uridine nucleosides. In aqueous media, results show that the binding is driven by hydrophobic interactions.  相似文献   

16.
以吲哚美辛(IDM)为模板分子,丙烯酰胺(AA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,本体聚合法制备过程中加入纳米胶体金,合成了吲哚美辛胶体金分子印迹聚合物(MIPs/Au),利用MIPs/Au表面胶体金对蛋白吸附作用,将抗吲哚美辛的多克隆抗体固定在MIPs/Au上,得到表面固定有抗体的新型聚合物(MIPs/Au-Ab)并对其进行了表征。制备了填充材料为MIPs/Au-Ab的固相萃取柱并对其上样、淋洗和洗脱条件进行了优化,并将所制备的新型萃取柱用于水样中IDM的分离富集。抗吲哚美辛抗体交联在聚合物表面,不仅增加了萃取柱的特异性吸附容量,而且有效地降低了MIP的非特异性吸附。  相似文献   

17.
印迹聚合物改性多壁碳纳米管固相萃取熊果酸   总被引:1,自引:0,他引:1  
以聚乙二醇改性的碳纳米管为基质,熊果酸为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁腈为引发剂,采用沉淀聚合法成功制备碳纳米管-印迹复合材料.采用红外光谱和扫描电镜研究该复合印迹材料的结构和形貌.结果表明,在碳纳米管表面接枝一层稳定且均匀的印迹材料.采用静态吸附实验研究此印迹材料的吸附性能,...  相似文献   

18.
Molecular imprinting made easy   总被引:4,自引:0,他引:4  
A simple method of molecular imprinting is presented that uses a single cross-linking monomer N,O-bismethacryloyl ethanolamine (NOBE) along with template, initiator, and solvent. This formulation eliminates the need for additional functional monomers and empirical optimization of relative ratios of functional monomers, cross-linkers, and template. In fact, utilization of NOBE alone often provides molecularly imprinted polymers (MIPs) with higher performance than MIPs incorporating functional monomer (e.g., methacrylic acid).  相似文献   

19.
Yueqi Liu 《Talanta》2010,80(5):1713-967
Three monodispersed, molecularly imprinted polymers (MIPs) for cinchonidine (CD) have been synthesized by precipitation polymerization. MIP1 was prepared using methacrylic acid (MAA) as a functional monomer and divinylbenzene (DVB) as a cross-linker and MIP2 was prepared with further addition of 2-hydroxyethyl methacrylate (HEMA) as a co-monomer. For the preparation of MIP3, core-shell type MIP, monodispersed DVB homopolymers, which are prepared by precipitation polymerization, were used as a core and CD-imprinted MAA-DVB copolymer phases were coated onto the core. Three MIPs synthesized gave monodispersed, spherical beads in micrometer sizes. The binding characteristics and molecular recognition properties of MIP1-3 were examined by Scatchard analysis and chromatographic studies. The association constant of CD with MIP1 was the highest among MIPs prepared, while that with MIP3 was the lowest. The template molecule, CD, was more retained than its stereoisomer, cinchonine, on the three MIPs, and the stereoseparation factor of 38 was obtained with MIP3.  相似文献   

20.
以氯霉素(CAP)为模板,2-乙烯基吡啶(2-Vp)为功能单体,四氢呋喃和离子液体1-丁基-3-甲基咪唑四氟硼酸盐[BMIm]BF4的混合溶液为反应溶剂,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,合成了氯霉素的分子印迹及非印迹聚合物。优化功能单体、不同溶剂对印迹聚合物吸附性能的影响,结果表明,以2-乙烯基吡啶为功能单体,四氢呋喃和离子液体[BMIm]BF4(体积比1∶1)作为反应溶剂合成的分子印迹聚合物对氯霉素具有高的吸附容量,良好的特异性识别性能。氯霉素分子印迹聚合物的印迹因子为2.6,进行吸附-解吸附循环5次后,氯霉素印迹聚合物的性能稳定,可重复使用。将制备的氯霉素分子印迹聚合物作为富集材料,应用于鸡蛋样品中氯霉素的检测,回收率可达62.3%~81.1%,准确性好。  相似文献   

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