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1.
Magnetic molecularly imprinted polymer nanoparticles for bisphenol A were prepared by coassembling magnetic nanoparticles and amphiphilic random copolymers. Under optimized conditions, bisphenol A as template molecules, magnetic molecularly imprinted polymer particles with regular morphology, small size, good monodispersity, and high content of OA‐Fe3O4 were prepared by the coassembly method using P(MMA‐co‐MAA) with monomer ratio of 9:1. These magnetic molecularly imprinted polymer particles could be rapidly collected by an external magnet within 1 min. The saturated adsorption capacity of the magnetic molecularly imprinted polymer for bisphenol A was 201.5 mg/g, and the imprinting factor was 2.5. The separation factors for bisphenol A to β‐estradiol, estriol, and diethylstilbestrol was 3.1, 2.9, and 3.7, respectively. Unlike assembling amphiphilic copolymer in the selective solvent, the coassembly process was simple and rapid. Therefore, the present work provided a facile and versatile approach to construct magnetic molecularly imprinted polymer nanoparticles under mild conditions.  相似文献   

2.
A new method for the selective extraction of p‐aminosalicylic acid from aqueous and urine samples has been developed using magnetic molecularly imprinted polymer nanoparticles before determination by high‐performance liquid chromatography. The Fe3O4 nanoparticles were first prepared through the chemical coprecipitation of Fe2+ and Fe3+ and then coated with a vinyl shell. Subsequently, a layer of molecularly imprinted polymers was grafted onto the vinyl‐modified magnetic nanoparticles by precipitation polymerization. FTIR spectroscopy, scanning electron microscopy, vibrating sample magnetometry, and thermogravimetric analysis were applied to characterize the sorbent properties. Moreover, the predominant parameters affecting the magnetic solid phase extraction such as sample pH, sorption and elution times, the amount of sorbent, and composition and volume of eluent were investigated thoroughly. The maximum sorption capacity of the imprinted polymer toward p‐aminosalicylic acid was 70.9 mg/g, which is 4.5 times higher than that of the magnetic nonimprinted polymer. The magnetic molecularly imprinted polymer nanoparticles were applied for the selective extraction of p‐aminosalicylic acid from aqueous and urine samples and satisfactory results were achieved. The results illustrate that magnetic molecularly imprinted polymer nanoparticles have a great potential in the extraction of p‐aminosalicylic acid from environmental and biological matrices.  相似文献   

3.
In this work, core/shell magnetic molecularly imprinted polymer nanoparticles were synthesized for extraction and pre‐concentration of valsartan from different samples and then it was measured with high‐performance liquid chromatography. For preparation of molecularly imprinted polymer nanoparticles, Fe3O4 nanoparticles were coated with tetraethyl orthosilicate and then functionalized with 3‐(trimethoxysilyl) propyl methacrylate. In the next step, molecularly imprinted polymer nanoparticles were synthesized under reflux and distillation conditions via polymerization of methacrylic acid, valsartan (as a template), azobisisobutyronitrile and ethylene glycol dimethacrylate as cross linking. The properties of molecularly imprinted polymer nanoparticle were investigated by FTIR spectroscopy, field emission scanning electron microscopy, and X‐ray diffraction. Box‐Behnken design with the aid of desirability function was used for optimizing the effect of variables such as the amounts of molecularly imprinted polymer nanoparticles, time of sonication, pH, and volume of methanol on the extraction percentage of valsartan. According to the obtained results, the affecting variables extraction condition were set as 10 mg of adsorbent, 16 min for sonication, pH = 5.5 and 0.6 mL methanol. The obtained linear response (r2 > 0.995) was in the range of 0.005–10 µg/mL with detection limit 0.0012 µg/mLand extraction recovery was in the range of 92–95% with standard deviation less than 6% (n = 3).  相似文献   

4.
We present a facile strategy to prepare the molecularly imprinted polymers layer on the surface of Fe3O4 nanoparticles with core‐shell structure via sol–gel condensation for recognition and enrichment of triclosan. The Fe3O4 nanoparticles were first synthesized by a solvothermal method. Then, template triclosan was self‐assembled with the functional monomer 3‐aminopropyltriethoxysilane on the silica‐coated Fe3O4 nanoparticles in the presence of ethanol and water. Finally, the molecularly imprinted polymers were formed on the surface of silica‐coated Fe3O4 nanoparticles to obtain the product. The morphology, magnetic susceptibility, adsorption, and recognition property of magnetic molecularly imprinted polymers were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffractometry, vibrating sample magnetometry, and re‐binding experiments. The magnetic molecularly imprinted polymers showed binding sites with good accessibility, fast adsorption rate, and high adsorption capacity (218.34 μg/g) to triclosan. The selectivity of magnetic molecularly imprinted polymers was evaluated by the rebinding capability of triclosan and two other structural analogues (phenol and p‐chlorophenol) in a mixed solution and good selectivity with an imprinting factor of 2.46 was obtained. The application of triclosan removal in environmental samples was demonstrated.  相似文献   

5.
The determination of morphine concentration in the blood and urine is necessary for patients and recruitment purposes. Herein, a magnetic molecularly imprinted polymer for selective and efficient extraction of morphine from biological samples was synthesized by using a core–shell method. Fe3O4 nanoparticles were coated with SiO2‐NH2. The molecularly imprinted polymer was coated on the Fe3O4/SiO2‐NH2 surface by the copolymerization of methacrylic acid and ethylene glycol dimethacrylate in the presence of morphine as the template molecule. The morphological and magnetic properties of the polymer were investigated. Field‐emission scanning electron microscopy indicated that the prepared magnetic polymer is almost uniform. The saturation magnetization values of Fe3O4 nanoparticles, Fe3O4/SiO2‐NH2, and the magnetic polymer were 48.41, 31.69, and 13.02 emu/g, respectively, indicating that all the particles are superparamagnetic. Kinetics of the adsorption of morphine on magnetic polymer were well described by second‐order kinetic and adsorption processes and well fitted by the Langmuir adsorption isotherm, in which the maximum adsorption capacity was calculated as 28.40 mg/g. The recoveries from plasma and urine samples were in the range of 84.9–105.5 and 94.9–102.8%, respectively. By using the magnetic molecularly imprinted polymer, morphine can selectively, reliably, and in low concentration be determined in biological samples with high‐performance liquid chromatography and UV detection.  相似文献   

6.
Magnetic molecularly imprinted polymer nanoparticles for di‐(2‐ethylhexyl) phthalate were synthesized by surface imprinting technology with a sol–gel process and used for the selective and rapid adsorption and removal of di‐(2‐ethylhexyl) phthalate from aqueous solution. The prepared magnetic molecularly imprinted polymer nanoparticles were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and vibrating sample magnetometry. The adsorption of di‐(2‐ethylhexyl) phthalate onto the magnetic molecularly imprinted polymer was spontaneous and endothermic. The adsorption equilibrium was achieved within 1 h, the maximum adsorption capacity was 30.7 mg/g, and the adsorption process could be well described by Langmuir isotherm model and pseudo‐second‐order kinetic model. The magnetic molecularly imprinted polymer displayed a good adsorption selectivity for di‐(2‐ethylhexyl) phthalate with respect to dibutyl phthalate and di‐n‐octyl phthalate. The reusability of magnetic molecularly imprinted polymer was demonstrated for at least eight repeated cycles without significant loss in adsorption capacity. The adsorption efficiencies of the magnetic molecularly imprinted polymer toward di‐(2‐ethylhexyl) phthalate in real water samples were in the range of 98–100%. These results indicated that the prepared adsorbent could be used as an efficient and cost‐effective material for the removal of di‐(2‐ethylhexyl) phthalate from environmental water samples.  相似文献   

7.
Atrazine contamination of water is of considerable concern because of the potential hazard to human health. In this study, a magnetic molecularly imprinted polymer for atrazine was prepared by the surface‐imprinting technique using Fe3O4 as the core, mesoporous silica as the carrier, atrazine as the template, and itaconic acid as the functional monomer. The magnetic molecularly imprinted polymer was characterized by Fourier‐transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, and vibration‐sample magnetometry. The binding properties of the magnetic molecularly imprinted polymer toward atrazine were investigated by adsorption isotherms, kinetics, and competitive adsorption. It was found that the adsorption equilibrium was achieved within 2 h, the maximum adsorption capacity of atrazine was 8.8 μmol/g, and the adsorption process could be well described by the Langmuir isotherm model and pseudo‐second‐order kinetic model. The magnetic molecularly imprinted polymer exhibited good adsorption selectivity for atrazine with respect to structural analogues, such as cyanazine, simetryne, and prometryn. The reusability of the magnetic molecularly imprinted polymer was demonstrated for at least five repeated cycles without a significant decrease in adsorption capacity. These results suggested that the magnetic molecularly imprinted polymer could be used as an efficient material for the selective adsorption and removal of atrazine from water samples.  相似文献   

8.
A dual responsive molecularly imprinted polymer sensitive to both photonic and magnetic stimuli was successfully prepared for the detection of four sulfonamides in aqueous media. The photoresponsive magnetic molecularly imprinted polymer was prepared by surface imprinting polymerization using superparamagnetic Fe3O4 nanoparticles functionalized with a silica layer as a support, water‐soluble 4‐[(4‐methacryloyloxy)phenylazo]benzenesulfonic acid as the functional monomer, and sulfadiazine as the template. The magnetic molecularly imprinted polymers showed specific affinity to sulfadiazine and its structural analogs in aqueous media. Upon alternate irradiation at 365 and 440 nm, the quantitative bind and release of the four sulfonamides by magnetic molecularly imprinted polymers occurred. Furthermore, the prepared magnetic molecularly imprinted polymers were used as solid‐phase extraction material selectively extracted the four sulfonamides from water samples with good recoveries. Thus, a simple, convenient, and reliable detection method for sulfonamides in the environment based on responsive magnetic molecularly imprinted polymers was successfully established.  相似文献   

9.
A protein imprinting approach for the synthesis of core–shell structure nanoparticles with a magnetic core and molecularly imprinted polymer (MIP) shell was developed using a simple distillation–precipitation polymerization method. In this work, Fe3O4 magnetic nanoparticles were first synthesized through a solvothermal method and then were conveniently surface‐modified with 3‐(methacryloyloxy)propyltrimethoxylsilane as anchor molecules to donate vinyl groups. Next a high‐density MIP shell was coated onto the surface of the magnetic nanoparticles by the copolymerization of functional monomer acrylamide (AAm), cross‐linking agent N,N′‐methylenebisacrylamide (MBA), the initiator azodiisobutyronitrile (AIBN), and protein in acetonitrile heated at reflux. The morphology, adsorption, and recognition properties of the magnetic molecularly imprinted nanoparticles were investigated by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), and rebinding experiments. The resulting MIP showed a high adsorption capacity (104.8 mg g?1) and specific recognition (imprinting factor=7.6) to lysozyme (Lyz). The as‐prepared Fe3O4@Lyz‐MIP nanoparticles with a mean diameter of 320 nm were coated with an MIP shell that was 20 nm thick, which enabled Fe3O4@Lyz‐MIP to easily reach adsorption equilibrium. The high magnetization saturation (40.35 emu g?1) endows the materials with the convenience of magnetic separation under an external magnetic field and allows them to be subsequently reused. Furthermore, Fe3O4@Lyz‐MIP could selectively extract a target protein from real egg‐white samples under an external magnetic field.  相似文献   

10.
A type of surface imprinting over magnetic Fe3O4 nanoparticles utilizing erythromycin‐A as a template for use in the separation and recovery of erythromycin was developed and investigated. As the intermolecular forces play a key role in the performance of imprinted materials, differential scanning calorimetry, and 1H NMR spectroscopy was employed to evaluate the interactions between erythromycin and the functional monomer β‐cyclodextrin. To synthesize the surface imprinted polymers, magnetic Fe3O4 nanoparticles, the core materials, were modified with a free radical initiator to initialize polymerization in a “grafting from” manner. Then using acryloyl‐modified β‐cyclodextrin as the functional monomer and ethyleneglycol dimethacrylate as the cross‐linker, thin erythromycin‐imprinted films were fabricated by the radical‐induced graft copolymerization of monomers on the surface of the Fe3O4 nanoparticles. Selectivity experiments showed that the erythromycin‐A‐imprinted materials had recognition ability toward erythromycin derivatives. Finally, these magnetic molecularly imprinted particles were successfully used for the separation and enrichment of erythromycin from the mother liquor. The recovery, detected by high‐performance liquid chromatography and differential pulse voltammetry, approached 97%. The combination of the specific selectivity of the imprinted material and the magnetic separation provided a powerful tool that is simple, flexible, and selective for the separation and recovery of erythromycin.  相似文献   

11.
One‐monomer molecularly imprinted magnetic nanoparticles were prepared as adsorbents for selective extraction of bisphenol A from water in this study. A single bi‐functional monomer was adopted for preparation of the molecularly imprinted polymer, avoiding the tedious trial‐and‐error optimizations as traditional strategy. Moreover, bisphenol F was used as the dummy template for bisphenol A to avoid the interference from residual template molecules. These nanoparticles showed not only large adsorption capacity and good selectivity to the bisphenol A but also outstanding magnetic response performance. Furthermore, they were successfully used as magnetic solid‐phase extraction adsorbents of bisphenol A from various water samples, including tap water, river water, and seawater. The developed method was found to be much more efficient, convenient, and economical for selective extraction of bisphenol A compared with the traditional solid‐phase extraction. Separation of these nanoparticles can be easily achieved with an external magnetic field, and the optimized adsorption time was only 15 min. The recoveries of bisphenol A in different water samples ranged from 85.38 to 93.75%, with relative standard deviation lower than 7.47%. These results showed that one‐monomer molecularly imprinted magnetic nanoparticles had the potential to be popular adsorbents for selective extraction of pollutants from water.  相似文献   

12.
Surface enrofloxacin‐imprinted magnetic nanoparticles were prepared for the selective recognition and fast separation of fluoroquinolones in human serum by surface‐initiated reversible addition fragmentation chain transfer polymerization. The surface morphology and imprinted behavior were investigated and optimized. The living/controlled nature of reversible addition‐fragmentation chain transfer polymerization reaction allowed the successful construction of well‐defined imprinted polymer layer outside the Fe3O4 core. Such molecularly imprinted polymers exhibited superparamagnetic properties and specific recognition toward fluoroquinolones. Combined with reversed‐phase high‐performance liquid chromatography, the prepared molecularly imprinted polymers were used for the selective enrichment and analysis of fluoroquinolones in human serum samples. The recoveries of four fluoroquinolones were 86.8–95.3% with relative standard deviations of 2.0–6.8% (n  = 3). Such magnetic molecularly imprinted polymers have great prospects in the separation and enrichment of trace analysts in complex biological samples.  相似文献   

13.
A novel type of magnetic molecularly imprinted polymer was prepared for the selective enrichment and isolation of chelerythrine from Macleaya cordata (Willd) R. Br. The magnetic molecularly imprinted polymers were prepared using functional Fe3O4@SiO2 as a magnetic support, chelerythrine as template, methacrylic acid as functional monomer, and ethylene glycol dimethacrylate as cross‐linker. Density functional theory at the B3LYP/6‐31G (d, p) level with Gaussian 09 software was applied to calculate the interaction energies of chelerythrine, methacrylic acid and the complexes formed from chelerythrine and methacrylic acid in different ratios. The structural features and morphology of the synthesized polymers were characterized by using Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, and vibration sample magnetometry. Adsorption experiments revealed that the magnetic molecularly imprinted polymers possessed rapid kinetics, high selectivity, and a higher binding capacity (7.96 mg/g) to chelerythrine than magnetic molecularly non‐imprinted polymers (2.36 mg/g). The adsorption process was in good agreement with the Langmuir adsorption isotherm and pseudo‐second‐order kinetics models. Furthermore, the magnetic molecularly imprinted polymers were successfully employed as adsorbents for the extraction and enrichment of chelerythrine from Macleaya cordata (Willd) R. Br. The results indicated that the magnetic molecularly imprinted polymers were suitable for the selective adsorption of chelerythrine from complex samples such as natural medical plants.  相似文献   

14.
In this work, a novel magnetic nanomaterial functionalized with a molecularly imprinted polymer was prepared for the extraction of protoberberine alkaloids. Molecularly imprinted polymers were made on the surface of Fe3O4 nanoparticles by using berberine as template, acetonitrile/water as porogen, acrylamide as functional monomer and ethylene glycol dimethacrylate as cross‐linker. The optimized molar ratio of template/functional monomer was 1:7. The polymeric magnetic nanoparticles were characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. The stability and adsorption capacity of the molecularly imprinted polymers were investigated. The molecularly imprinted polymers were used as a selective sorbent for the magnetic molecularly imprinted solid‐phase extraction and determination of jatrorrhizine, palmatine, and berberine. Extraction parameters were studied including loading pH, sample volume, stirring speed, and extraction time. Finally, a magnetic molecularly imprinted solid‐phase extraction coupled to high‐performance liquid chromatography method was developed. Under the optimized conditions, the method showed good linear range of 0.1–150 ng/mL for berberine and 0.1–100 ng/mL for jatrorrhizine and palmatine. The limit of detection was 0.01 ng/mL for berberine and 0.02 ng/mL for jatrorrhizine and palmatine. The proposed method has been applied to determine protoberberine alkaloids in Cortex phellodendri and rat plasma samples. The recoveries ranged from 87.33–102.43%, with relative standard deviation less than 4.54% in Cortex phellodendri and from 102.22–111.15% with relative standard deviation less than 4.59% in plasma.  相似文献   

15.
A novel magnetic molecularly imprinted polymer adsorbing material was successfully synthesized to detect ribavirin in animal feedstuff. Molecularly imprinted polymer was prepared through surface polymerization by using ribavirin as template molecule, methyl methacrylate, and γ‐methacryloxypropyl trimethoxy silane functionalized magnetic mesoporous silica as bifunctional monomers, and ethylene diglycidyl ether as crosslinking agent. The prepared magnetic molecularly imprinted polymer was characterized by scanning electron microscopy and infrared spectroscopy. Static and dynamic adsorption experiments and selective adsorption analysis were performed to evaluate the adsorption and selectivity of magnetic molecularly imprinted polymer. Different experiments were conducted to optimize the magnetic solid‐phase extraction conditions. Under optimal experimental conditions, a magnetic molecularly imprinted solid‐phase extraction coupled with high‐performance liquid chromatography method was successfully developed for ribavirin detection. The established method achieved a satisfactory linear range of 0.20–50 mg/L (R> 0.99) and a low detection limit (0.081 mg/kg). An average recovery of 92–105% with relative standard deviation of <6.5% was obtained upon the application of the developed method to detect ribavirin in real feedstuff samples. Thus, established method can be used for the rapid and simple separation and detection of added ribavirin in feedstuff.  相似文献   

16.
A molecularly imprinted polymer was selectively applied for solid‐phase extraction and diazinon residues enrichment before high‐performance liquid chromatography. Diazinon was thermally copolymerized with Fe3O4@polyethyleneglycol nanoparticles, methacrylic acid (functional monomer), 2‐hydroxyethyl methacrylate (co‐monomer), and ethylene glycol dimethacrylate (cross‐linking monomer) in the presence of acetonitrile (porogen) and 2,2‐azobisisobutyronitrile (initiator). Then, the imprinted diazinon was reproducibly eluted with methanol/acetic acid (9:1, v/v). The sorbent particles were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The comprehensive study of variables through experimental design showed that the maximum performance was achieved under these conditions: pH 7, 10 mL sample volume, 15 mg sorbent, 10 min vortex time, 5 min ultrasonic time, 200 μL methanol/acetic acid (9:1, v/v) as eluent, and 5 min desorption time. Under optimized conditions, the molecularly imprinted polymer solid‐phase extraction method demonstrated a linear range (0.02–5 g/mL), a correlation coefficient of 0.997, and 0.005 g/mL detection limit.  相似文献   

17.
Polydopamine‐coated Fe3O4 magnetic nanoparticles synthesized through a facile solvothermal reaction and the self‐polymerization of dopamine have been employed as a magnetic solid‐phase extraction sorbent to enrich four phenolic compounds, bisphenol A, tetrabromobisphenol A, (S)‐1,1′‐bi‐2‐naphthol and 2,4,6‐tribromophenol, from environmental waters followed by high‐performance liquid chromatographic detection. Various parameters of the extraction were optimized, including the pH of the sample matrix, the amount of polydopamine‐coated Fe3O4 sorbent, the adsorption time, the enrichment factor of analytes, the elution solvent, and the reusability of the nanoparticles sorbent. The recoveries of these phenols in spiked water samples were 62.0–112.0% with relative standard deviations of 0.8–7.7%, indicating the good reliability of the magnetic solid‐phase extraction with high‐performance liquid chromatography method. In addition, the extraction characteristics of the magnetic polydopamine‐coated Fe3O4 nanoparticles were elucidated comprehensively. It is found that there are hydrophobic, π–π stacking and hydrogen bonding interactions between phenols and more dispersible polydopamine‐coated Fe3O4 in water, among which hydrophobic interaction dominates the magnetic solid‐phase extraction performance.  相似文献   

18.
A novel dispersive admicelle solid‐phase extraction method based on sodium dodecyl sulfate‐coated Fe3O4 nanoparticles was developed for the selective adsorption of berberine, coptisine, and palmatine in Gegen‐Qinlian oral liquid before high‐performance liquid chromatography. Fe3O4 nanoparticles were synthesized by a chemical coprecipitation method and characterized by using transmission electron microscopy. Under acidic conditions, the surface of Fe3O4 nanoparticles was coated with sodium dodecyl sulfate to form a nano‐sized admicelle magnetic sorbent. Owing to electrostatic interaction, the alkaloids were adsorbed onto the oppositely charged admicelle magnetic nanoparticles. The quick separation of the analyte‐adsorbed nanoparticles from the sample solution was performed by using Nd‐Fe‐B magnet. Best extraction efficiency was achieved under the following conditions: 800 μL Fe3O4 nanoparticles suspension (20 mg/mL), 150 μL sodium dodecyl sulfate solution (10 mg/mL), pH 2, and vortexing time 2 min for the extraction of alkaloids from 10 mL of diluted sample. Four hundred microliters of methanol was used to desorb the alkaloids by vortexing for 1 min. Satisfactory extraction recoveries were obtained in the range of 85.9–120.3%, relative standard deviations for intra‐ and interday precisions were less than 6.3 and 10.0%, respectively. Finally, the established method was successfully applied to analyze the alkaloids in two batches of Gegen‐Qinlian oral liquids.  相似文献   

19.
In this study, a novel magnetic nanoadsorbent was synthesized by grafting β‐cyclodextrin onto the modified surface of Fe3O4 nanoparticles for the sorption and extraction of sertraline hydrochloride from human biological fluids. The extracted sertraline hydrochloride was measured by high‐performance liquid chromatography. The grafted nanosorbent was confirmed by Fourier transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis, and elemental analysis. The kinetic sorption of sertraline hydrochloride by magnetic nanosorbent was 1 h. The best temperature for sorption of sertraline hydrochloride was at 25°C at an optimum pH of 5. The adsorbed sertraline hydrochloride can be desorbed by using methanol solution containing acetic acid (5%) and trifluoroacetic acid (1%).  相似文献   

20.
In this paper, temperature and pH‐sensitive interpenetrating polymer network (IPN) nanogels (NGs) were firstly prepared, and magnetic hybrid NGs were made through in‐situ precipitation of Fe2+ and Fe3+ into the IPN NGs. Under the optimized condition, the resulting hybrid NG dispersion with up to 17.3 wt% magnetite was stable, while the size distribution of the NGs is broad due to the formation of Fe3O4 nanoparticles outside the NGs. In order to synthesize relatively uniform magnetic NGs, magnetite content was reduced to 8.1 wt% magnetite. The NGs with 8.1 wt% magnetite can quickly self‐assemble into colloidal crystals induced by magnet, while such NGs slowly self‐assembled into colloidal crystals without external magnetic field. Furthermore, the reflection wavelength of the self‐assembled magnetic NGs showed red‐shift with increasing pH and temperature.  相似文献   

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