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1.
Enantioselective membrane was prepared using nitrocellulose as membrane material. The flux and permselective properties of membrane using water solution of D ,L ‐tyrosine as feed solution were studied. The top surface and cross‐section morphology of the resulting membrane were examined by scanning electron microscopy. The optical resolution of over 85% enantiomeric excess was achieved when the enantioselective membrane was prepared with 25 wt % nitrocellulose and 15 wt % N,N‐dimethylformamide in the casting solution of methanol, 10°C temperature of water bath for the gelation of the membrane, and the operating pressure and the feed concentration of the D ,L ‐tyrosine were 6 kgf/cm2 and 0.25 mg/mL, respectively. Since the nitrocellulose contains a large amount of chirality active carbons on the backbone structure and is possible to form helical structure, it is considered to be the reason for the enantioselectivity of the membrane. This is the first report that nitrocellulose can be used as a membrane material. This work indicates that the large‐scale purification of chiral molecules from racemic mixtures will be realized by the enantioselective membrane technique in the near future and that the enantioselective nitrocellulose membrane could soon become very attractive for industrial uses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

2.
Molecularly imprinted latex membrane (MILM) is prepared by core‐shell emulsion technique in the presence of a template molecule (L ‐Tryptophan). A hard inward and soft outward microstructure latex particle is designed to obtain MILM with both flexibility and impact strength. Molecularly imprinted layer with high crosslinking degree is grafted on the surface of core‐shell latex particles. NaCl, glucose, urea, polyethylene glycol, Mw 300, etc., are added during the film‐forming process to produce porous microstructure in MILM. Fourier transform infrared spectroscopy (FTIR) and Scatchard analysis are used to investigate the interaction between L ‐Tryptophan and MILM and the binding ability of the resultant MILM, respectively. The functional binding and separation performances in aqueous medium towards template are carried out. The results reveal that the content and type of porogen and the shell composition have significant effects on adsorption capacity and separation ability. MILM with glucose as porogen shows high recognition towards the template with adsorption separation factor reaching 9.06. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

3.
A uniformly sized molecularly imprinted polymer for the peripheral vasodilator drug tolazoline (T‐MIP) was prepared, and a nonimprinted polymer (NIP) was also synthesized in the same way but in the absence of the template. The T‐MIP was prepared with methylacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker by a multistep swelling and polymerization method. These imprinted materials were characterized by scanning electron microscopy, nitrogen adsorption, and static adsorption experiments. Binding studies were also performed to evaluate the uptake of T‐MIP and NIP with the results that T‐MIP had a significantly higher binding capacity for tolazoline (T) than did NIP. The maximum static adsorption capacities of T‐MIP and NIP for T were 78.9 and 38.8 μmol/g, respectively. The T‐MIPs and NIPs were used as stationary phases of solid‐phase extraction (SPE), and a relative selectivity coefficient (k′) value of 5.21 was obtained, which showed that the T‐MIP sorbent had higher selectivity than the NIP sorbent. The method was applied to the determination of T in urine samples. The prepared polymer sorbent showed promise for SPE for gas chromatography determination of T in urine samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

4.
The effects of membrane structure on the separation of L ‐phenylalanine (L ‐Phe) by electrodialysis from a fermentation broth and on the fouling tendency were investigated in this study. Two anion‐exchange membranes (Neosepta AFX and AM‐1, Tokuyama, Japan) were selected and characterized using the chronopotentiometry method. For a fresh membrane, AFX showed a lower electrical resistance and a lower permselectivity than AM‐1. After being fouled with humic acid, however, the electrical resistance of AFX was higher than that of AM‐1. The L ‐Phe selectivities for both membranes were lower than those of the fresh membranes. The result may be attributed to the structural difference between AFX and AM‐1 membranes. AFX has a lower repulsion force against the co‐ion and could be more strongly affected by the foulants than AM‐1 because AFX has a more porous structure than AM‐1. Experiments on the separation of L ‐Phe from the fermentation broth were carried out using two different stack configurations, ie desalting electrodialysis and water‐splitting electrodialysis. It was observed that the recovery efficiency of L ‐Phe through electrodialysis for 100 min reached 95% for AFX and 85% for AM‐1. In the desalting configuration of electrodialysis, the solution pH must be adjusted to alkaline conditions to recover the L ‐Phe through the anion‐exchange membrane. On the contrary, it was possible to recover the L ‐Phe without adjustment of the solution pH in the water‐splitting electrodialysis because OH? generated from the bipolar membrane converted neutral L ‐Phe into an anion. © 2002 Society of Chemical Industry  相似文献   

5.
Molecular imprinting is an elegant approach to induce antibody like recognition ability in synthetic polymers. The technique of molecular imprinting has been used extensively in the preparation of tailor‐made stationary phases in chromatography, sorbents in solid phase extraction, sensor elements, etc. Though several of the reported molecularly imprinted polymers (MIPs) possess substrate selectivity comparable to antibodies, they are poor in adsorption capacity. The adsorption capacity could be improved presumably through enhanced interaction between the functionalities of the monomers and the print molecule. A simple approach to improve the interaction is perhaps the use of chemically modified monomers in the synthesis of the MIPs. This article explores this possibility by using a metal‐containing monomer in the synthesis of MIP. The data obtained using a copper acrylate based MIP and cholesterol as substrate indicates the adsorption capacity can be improved considerably through the simple chemical modification of the functional monomer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2795–2799, 2001  相似文献   

6.
Molecularly imprinted polymeric membranes were prepared from cellulose acetate (CA), of which acetyl content was 40%, by applying the alternative molecular imprinting technique. The Z‐d ‐Glu imprinted polymeric membranes thus obtained recognized d ‐Glu in preference to l ‐Glu from racemic Glu mixtures and vice versa. The affinity constants between Glu and the chiral recognition site for two kinds of membranes were determined to be 3.1 × 103 mol−1 dm3 from the adsorption isotherm of d ‐Glu or L ‐Glu in the molecularly imprinted CA membranes. Enantioselective electrodialysis was attained with the present membranes reflecting their adsorption selectivity. d ‐Glu was preferentially permeated through the Z‐d ‐Glu imprinted CA membrane, whereas L ‐Glu was permeated through the Z‐L ‐Glu imprinted CA membrane. The present study suggests that the molecularly imprinted CA membranes are applicable to the optical resolution of racemic amino acids. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 493–499, 1999  相似文献   

7.
Similar to those in complementary nucleotides' base pairs, we present a novel molecularly imprinted electrochemical sensor for emodin, constructed using a multiple hydrogen bonds strategy. We obtained the sensor by in situ photopolymerization, using allobarbital as a new functional monomer. We optimized the conditions of membrane imprinting and the composition of adsorption solvent. This artificial receptor exhibits high selectivity for the template in comparison with closely related analogs, aloin A and simetryne. The sensor was successfully applied in determination of emodin levels in one of the traditional Chinese medicines, the content of emodin in Sanhuang tablets detected using the voltammetric sensor and high performance liquid chromatography (HPLC) were 0.249 ± 0.009 (mg/tablet) and 0.246 ± 0.007 (mg/tablet), respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

8.
Uniform molecularly imprinted polymer beads were synthesized by precipitation polymerization for separation of triazine herbicides. A series of imprinted polymers were prepared using ametryn as template and divinylbenzene as crosslinking monomer, in combination with three different functional monomers under different solvent conditions. Under optimized reaction conditions, we obtained uniform molecularly imprinted polymer microspheres that display favorable molecular binding selectivity for triazine herbicides. The imprinted polymer beads synthesized using methacrylic acid as functional monomer in a mixture of methyl ethyl ketone and heptane showed the best results in terms of particle size distribution and molecular selectivity. Compared with nonimprinted polymer microspheres, the imprinted microspheres displayed significantly higher binding for a group of triazine herbicides including atrazine, simazine, propazine, ametryn, prometryn, and terbutryn. For the first time, precipitation polymerization has been used to produce highly uniform imprinted microspheres suitable for affinity separation of triazine herbicides. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

9.
A dummy molecularly imprinted polymers (DMIP) for phenol was synthesized by a thermal polymerization method with acrylamide as the functional monomer, ethylene dimethacrylate as the crosslinker, 2,2‐azobisisobutyronitrile as the free‐radical initiator, acetonitrile as the porogenic solvent, and sulfadiazine, a phenol analogue, as the template. In comparison to other adsorbents, the synthesized DMIP showed a higher capacity and rate of adsorption. The adsorption amount of the DMIP adsorbents for phenol reached 6.09 ± 0.15 mg/g, and the adsorption rate of the DMIP was about 0.406 ± 0.01 mg g?1·min?1. The results indicate that the Freundlich model fit the adsorption model of DMIP for phenol. The adsorption model of DMIP for phenol was multilayer adsorption. This showed that the DMIP synthesized by bulk polymerization could be used as a novel adsorbent for the removal of phenol from contaminated water. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

10.
A molecularly imprinted composite membrane (MICM) with pH‐controllability and selectivity to podophyllotoxin (PPT) was prepared using a polyvinylidene fluoride (PVDF) microfiltration membrane as the support. The functional monomer is 1‐phenyl‐3‐methyl‐4‐methacryloyl‐5‐pyrazolone (PMMP), which is a new β‐diketone compound with enol/ketol tautomerization. In this study, imprinting parameters, including the amounts of functional monomer and cross‐linker, and immersion time of membrane in the imprinting solution, were optimized by equilibrium adsorption experiments. Pore structure and surface morphology of the optimal MICM (MICM2) was characterized. Finally, competitive permeability of PPT in the presence of its analog 4′‐demethylpodophyllotoxin (DMEP) was measured under the drive of concentration difference. The results reveal that the surface morphology and pore structure of MICM2 are structurally different from those of the control nonimprinted membrane. As a result, MICM2 could efficiently recognize PPT in a complex system due to a better structural matching and the interaction between the functional groups of MICM2 and PPT. However, the most interesting finding is its pH‐controllability. The membrane could switch the preference to either PPT or DMEP with the change of pH values in the sample solution. At pH values smaller than 8.4, it led to a faster transportation of PPT, while the situation reversed to DMEP at pH values greater than 8.4. This peculiar property would lead this imprinted membrane to have potential application in the separation and enrichment of PPT, and the new functional monomer PMMP exhibited an attractive application prospect in the functional material fields. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

11.
Molecularly imprinted polymer (MIP) with Nα‐protected amino acid as the print molecule was prepared and used as the stationary phase for the chromatographic study of molecular recognition. Particles of MIP were prepared by photopolymerization of 4‐vinylpyridine in the presence of tert‐butyloxycarbonyl‐L ‐tyrosine (Boc‐L ‐Tyr) and packed into a column for the chromatographic resolution of Boc‐L ‐Tyr and tert‐butyloxycarbonyl‐L ‐phenylalanine (Boc‐L ‐Phe). These two Nα‐protected amino acids that differ from each other in the side chain with one hydroxyl group on the benzene ring could be well separated on the MIP. A separation factor of about two was achieved by using a mixture of acetonitrile (99.5 v/v %) and acetic acid (0.5 v/v %) as the mobile phase. Results suggest that the interaction between hydroxyl group in the side chain of amino acid and pyridine in the polymer dominated the selective adsorption of print molecule on the MIP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

12.
The multiple bulk copolymerization method, which was developed in our previous works, was further investigated with prometryn, tetracycline, and propranolol as templates for the preparation of molecularly imprinted polymer (MIP) coatings on silicon fibers for solid‐phase microextraction. The preparation conditions (e.g., the solvent, monomer, crosslinker, component proportions, polymerization time, and number of coating procedures) were investigated systemically in an effort to enhance the coating thickness, surface morphology, and reproducibility. The methodology was examined, and some common specialties were explored in the preparation of three MIP‐coated fibers. Even after the coating procedure was repeated 10 times, the prometryn, tetracycline, and propranolol MIP‐coated fibers were prepared reproducibly with coating‐thickness relative standard deviations of 2.6, 3.0, and 5.1%, respectively; they were highly homogeneous, and a compact morphological structure was obtained. The extraction capacities of prometryn, tetracycline, and propranolol with corresponding MIP‐coated fibers were approximately 10.4, 3.9, and 3.3 times as much as those with the nonimprinted polymer (NIP)‐coated fibers, respectively, and the selectivity factors of prometryn, tetracycline, and propranolol MIP coatings for the template molecules and structural analogues were 2.2–10.4, 2.2–3.9, and 1.3–3.3, respectively, in comparison with the corresponding NIP coatings. In comparison with commercial polydimethylsiloxane/divinylbenzene coatings that were approximately 3 times thicker, the extracted amounts of prometryn, tetracycline, and propranolol were 4.2, 12.3, and 7.7 times higher with prometryn, tetracycline, and propranolol MIP coatings, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

13.
The effect of poly(D ,L ‐lactide‐copara‐dioxanone) (PLADO) as the compatibilizer on the properties of the blend of poly(para‐dioxanone) (PPDO) and poly(D ,L ‐lactide) (PDLLA) has been investigated. The 80/20 PPDO/PDLLA blends containing from 1% to 10% of random copolymer PLADO were prepared by solution coprecipitation. The PLADO component played a very important role in determining morphology, thermal, mechanical, and hydrophilic properties of the blends. Addition of PLADO into the blends could enhance the compatibility between dispersed PDLLA phase and PPDO matrix; the boundary between the two phases became unclear and even the smallest holes were not detected. On the other hand, the position of the Tg was composition dependent; when 5% PLADO was added into blend, the Tg distance between PPDO and PDLLA was shortened. The blends with various contents of compatibilizer had better mechanical properties compared with simple PPDO/PDLLA binary polymer blend, and such characteristics further improved as adding 5% random copolymers. The maximum observed tensile strength was 29.05 MPa for the compatibilized PPDO/PDLLA blend with 5% PLADO, whereas tensile strength of the uncompatibilized PPDO/PDLLA blend was 14.03 MPa, which was the lowest tensile strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

14.
This study focus on the effect of the porogenic solvent on the morphology, recognition, and drug release of carbamazepine‐molecularly imprinted polymer nanospheres prepared by precipitation polymerization. The scanning electron microscopy (SEM) images and Brunauer‐Emmett‐Teller (BET) analysis showed that molecularly imprinted polymer (MIP) prepared by acetonitrile exhibited a regular spherical shape at the nanoscale with a high degree of monodispersity, specific surface area of 242 m2 g−1, and pore volume of 1 mL g−1, while those using chloroform and toluene produced irregular polymer particles with low specific surface area and pore volume. MIP prepared by acetonitrile/chloroform (1 : 1, v/v) showed mediator texture properties compared to MIPs obtained by acetonitrile or chloroform. Results from saturation and displacement assays indicated that the imprinted nanospheres with binding capacity of 2.85 (mg CBZ/g polymer) had high specific affinity to CBZ in contrast to nonimprinted nanospheres (1.63 mg CBZ/g polymer). The imprinted nanospheres with 2.4 selectivity factor had good recognition to CBZ than analog template of oxcarbazepine. Moreover, release studies showed that 20% of loaded CBZ was released from the imprinted nanospheres within the initial 6 h, while another 80% of CBZ was released in the following 9 days. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

15.
Using tribenuron‐methyl as a template and N,O‐bismethacryloyl ethanolamine as a functional crosslinking monomer, a molecularly imprinted nanowire membrane was prepared over an anodic alumina oxide membrane. The nanowire fabric of the imprinted membrane was established with a scanning electron microscope and a transmission electron microscope. However, the nonimprinted particulate membrane is formed in the absence of a template. Scatchard analysis showed that an equal class of binding sites were formed in the imprinted nanowire membrane and the dissociation constant and the maximum number of these binding sites were estimated to be 1.44 × 10−5 M and 22.7 µmol/g, respectively. The permeation experiments throughout the imprinted membrane and the nonimprinted one were carried out in a solution containing the template and its competitive analogs. These results demonstrated that the molecularly imprinted nanowire membrane exhibited higher transport selectivity for the template tribenuron‐methyl than its analogs, chlorimuron‐ethyl, thifensulfuron‐methyl and N‐(4‐bromophenylcarbamoyl)‐5‐chloro‐1H‐benzo[d]imidazole‐2‐carboxamide. But the nonimprinted granular membrane had no permselectivity for the four substrates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

16.
Poly(D ,L ‐lactide) (PDLLA) was synthesized by microwave‐irradiated ring‐opening polymerization catalyzed by stannous octoate (Sn(Oct)2) under atmosphere. The effects of heating medium, monomer purity, catalyst concentration, microwave irradiation time, and vacuum level were discussed. Under the appropriate conditions such as carborundum (SiC) as heating‐medium, 0.15% catalyst, lactide with purity above 99.9%, 450 W microwave power, 30 min irradiation time, and atmosphere, PDLLA with a viscosity–average molecular weight (Mη) over 2.0 × 105 and a yield over 85% was obtained. The dismission of vacuum to ring‐opening polymerization of D ,L ‐lactide (DLLA) under microwave irradiation simplified the process greatly. The temperature under microwave irradiation and conventional heating was compared. The largely enhanced ring‐opening polymerization rate of DLLA under microwave irradiation was the coeffect of thermal effects and microwave effects. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2244–2247, 2006  相似文献   

17.
Novel chiral polyureas were prepared from L ‐lysine‐4‐nitroanilide and 2,4‐toluene diisocyanate. The polyurea thus prepared gave a durable self‐standing membrane that can be directly converted into molecular recognition membranes by applying an alternative molecular imprinting. The Z‐D ‐glutamic acid (D ‐Glu) molecularly imprinted membrane adsorbed D ‐Glu in preference to L ‐glutamic acid (L ‐Glu) from racemic mixture of Glu and vice versa. Those two types of molecularly imprinted membrane showed optical resolution ability, adopting a concentration gradient as a driving force for membrane transport. A facile method to predict permselectivity of racemic mixture of charged permeant was proposed. From the observed membrane resistance, the permselectivity was predicted. The predicted permselectivity coincided with the observed one. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

18.
A novel cholesterol‐imprinted polymer (CMIP‐H) was prepared by a hybrid method of covalent imprinting and non‐covalent imprinting. This approach involves the copolymerization of a template‐containing monomer, cholesteryl 2‐hydroxyethyl methacrylate carbonate, and a cross‐linker, followed by hydrolysis to afford a flexible guest‐binding site accompanied with the easy and efficient removal of a ‘sacrificial spacer’. The effect of solvent on the binding capacity of CMIP‐H towards cholesterol was studied, indicating that a good binding capacity towards cholesterol could be achieved in a less‐polar solvent. The binding experiments of CMIP‐H towards a series of structural analogues of cholesterol, including cholesterol acetate, progesterone and stigmasterol, were carried out in hexane. The results showed that CMIP‐H almost did not bind cholesterol acetate at all because the hydrogen‐bonding site is blocked. It exhibited a similar binding towards both cholesterol and stigmasterol, but much higher binding towards progesterone. Copyright © 2005 Society of Chemical Industry  相似文献   

19.
Uniformly sized molecularly imprinted polymers (MIPs) for nimodipine have been prepared in an aqueous system by multi‐step swelling and polymerization method, utilizing 4‐vinylpyridine (4‐VPY) or methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EDMA) as a cross‐linking agent. Scanning electron microscopy was used to identify the structure features of the obtained polymers. Further, the influences of some chromatographic conditions were examined to explore the possible recognition mechanism. The results reveal that stable molecularly imprinted polymeric microspheres with good size monodispersity were obtained, and the polymer beads showed specific recognition for the template molecule and some other dihydropyridine calcium antagonists (DHPs). Besides hydrophobic interaction, the molecular shape complementation of DHPs and the MIPs seems to play an important role in the retention and recognition of DHPs. The Scatchard analysis showed that two kinds of binding sites existed in the MIPs. The MIPs was then used as a high‐performance liquid chromatography (HPLC) separation medium to simultaneously concentrate and purify nimodipine in plasma. The results reveal that the obtained MIPs could be used for on‐line concentration, purification, and measurement of nimodipine in biological samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

20.
A novel molecularly imprinted polymer based on tert‐butyl acrylate (MIP‐BA) was fabricated with the assistance of a cobalt(III)‐based catalyst bearing an N‐salicylidene isopropylamine ligand [(SPA)2CoCl]. After initiation with methyl aluminoxane, the catalyst system was found to be active toward the polymerization of tert‐butyl acrylate (t‐BA) in the presence of a polar template (Cibacron reactive red dye) and divinylbenzene (DVB) as a crosslinker. Polymerization experiments, including those of t‐BA, t‐BA, and DVB and t‐BA and dye, were also carried out. Isolated blank polymers and MIP‐BA were analyzed with a variety of techniques, including differential scanning calorimetry, thermogravimetric analysis, gel permeation chromatography, infrared spectroscopy, nuclear magnetic resonance, and ultraviolet–visible spectroscopy. In general, the complex showed moderate polymerization activity and produced high‐molar‐mass poly(tert‐butyl acrylate); however, a decrease in the monomer conversion was observed upon the addition of the dye and/or the crosslinker. The effect of imprinting was obvious when the adsorption capacity of MIP‐BA measured at pH 6 for red dye (the imprinted molecule) was increased from 9.2 to 90.4 mg/g after imprinting. Competitive adsorption studies revealed that the dye‐imprinted polymer enabled the efficient uptake of red dye, even in the presence of blue and yellow dyes that had similar chemical structures to the imprinted molecule. The selectivity coefficients were 43 and 36 with respect to the blue and yellow dyes, respectively. The proposed polymerization procedure could be extended to other anionic polar reactive dyes and polar reactive polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

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