氏名　パチャラパリ　スレニバスル　レディ
学位の種類　博士（工学）
学位記番号　博甲第230号
学位授与の日付　平成13年3月26日
学位論文題目　Molecular Recognition Characteristics of Various Imprinted Polymer Materials （各種インプリント高分子の分子認識特性）
論文審査委員
　主査　教授　藤井　信行
　副査　助教授　小林　高臣
　副査　教授　野坂　芳雄
　副査　教授　塩見　友雄
　副査　助教授　下村　雅人

• 論文目次
• 論文要旨

［平成12（2000）年度博士論文題名一覧］ ［博士論文題名一覧］に戻る．

Acknowledgements　p.i

List of Figures　p.ii

List of Tables　p.v

List of Glossary　p.vi

Abstract　p.viii

General Introduction　p.1

Molecular recognition　p.1

Molecularly imprinted polymers　p.1

Rationale of molecular imprinting　p.2

Progress in molecular imprinting　p.3

Chromatography　p.4

Catalysis　p.4

Metal-imprinting　p.5

Bio-imprinting　p.5

Sensors　p.5

Solid phase extraction　p.6

Imprinted membranes　p.6

Poly（amide-imide）s　p.7

Scope of the present investigation　p.8

References　p.9

Chapter 1. Molecularly Imprinted Polyamide Nylon-6 Utilizing Amide Hydrogen Bonding Interactions for the Recognition of Amino Acids　p.13
1.1.　Introduction　p.13
1.2.　Experimental　p.14
1.2.1.　Techniques/Measurements　p.14
1.2.2.　Materials　p.15
1.2.3.　Molecularly imprinted membrane preparation　p.16
1.2.4.　Recognition experiments for amino acids　p.16
1.2.5.　Ultrafiltration permeation and recognition experiments　p.16
1.3.　Results and Discussion　p.17
1.3.1.　FT-IR spectral analysis　p.17
1.3.2.　Recognition characteristics　p.19
1.3.3.　Saturation binding curves　p.19
1.3.4.　Binding phenomena　p.20
1.3.5.　Membrane transport measurements　p.21
1.4.　Summary　p.22
1.5.　References　p.23

Chapter 2. Molecularly imprinted Polyamide -6 forRacemic Separation of Phenylalanine　p.24
2.1.　Introduction　p.24
2.2.　Experimental　p.25
2.2.1.　Ultrafiltration permeation and recognition experiments　p.25
2.3.　Results and Discussion　p.25
2.3.1.　FT-IR spectral analysis of imprinted-Nylon-6　p.25
2.3.2.　Phenyalalanine recognition characteristics　p.26
2.3.3.　Effect of template concentration in substrate recognition　p.27
2.3.4.　Saturation binding curves　p.28
2.4.　Summary　p.29
2.5.　References　p.30

Chapter 3. Recognition Characteristics of Dibenzofuran Analogues by Molecularly Imprinted Polymers　p.31
3.1.　Introduction　p.31
3.2.　Experimental　p.32
3.2.1.　Materials　p.32
3.2.2.　Preparation and characterization of imprinted polymers　p.32
3.2.3.　Recognition experiments　p.34
3.3.　Results and Discussion　p.34
3.3.1.　FT-IR spectral analysis　p.34
3.3.2.　Recognition characteristics for DBF analogues　p.36
3.3.3.　Saturation binding of DBF imprinted polymers　p.37
3.3.4.　Template selectivity and substrate recognition　p.38
3.4.　Summary　p.40
3.5.　References　p.40

Chapter 4. Solvent Role in the Molecular Recognition Characteristics of Dibenzofuran Analogues by the Imprinted Polymers　p.42
4.1.　Introduction　p.42
4.2.　Experimental　p.43
4.2.1.　Template and substrate recognition　p.43
4.3.　Results and Discussion　p.43
4.3.1.　Solvent role in recognition characteristics　p.43
4.3.2.　Dibenzofuran analogues recognitions in water media　p.43
4.3.3.　Recognition characteristics in mixture of methanol-water media　p.45
4.3.4.　Saturation binding in methanol-water media　p.45
4.3.5.　Substrates recognition　p.46
4.3.6.　Other substrates recognition　p.46
4.4.　Summary　p.47
4.5.　References　p.48

Chapter 5. Molecular Recognition of Dibenzofuran Analogues by the Imprinted Functional Copolymers　p.49
5.1.　Introduction　p.49
5.2.　Experimental　p.50
5.3.　Results and Discussion　p.51
5.3.1.　Substrate saturation binding characteristics of copolymers　p.52
5.3.2.　Other substrates recognition　p.53
5.4.　Summary　p.54
5.5.　References　p.54

Chapter 6. Ultrafiltration Permeation and Recognition Behavior of Dibenzofuran Analogues by the Imprinted Polysulfone　p.55
6.1.　Introduction　p.55
6.2.　Experimental　p.56
6.3.　Results and Discussion　p.56
6.3.1.　Recognition characteristics by the PSf membrane in permeation mode　p.56
6.3.2.　Template concentration effect in recognition properties　p.57
6.4.　Summary　p.58
5.5.　References　p.58

Chapter 7. Synthesis and Characterization of Novel Aromatic Poly（amide-imide）s with Alternate （amide-amide） and （imide-imide） Sequences　p.59
7.1.　Introduction　p.59
7.2.　Experimental　p.60
7.2.1.　Materials　p.60
7.2.2.　Synthesis of monomers　p.60
7.2.3.　Synthesis of poly（amide-imide）s　p.61
7.2.4.　Measurements　p.62
7.3.　Results and Discussion　p.62
7.3.1.　Preparation of diamine amic acids　p.62
7.3.2.　Polymer synthesis　p.64
7.3.3.　Polymer characterization　p.64
7.3.4.　Thermal properties　p.66
7.4.　References　p.66
　Summary　p.68
　List of Publications　p.71
　Presentations in Conferences/Symposiums　p.72

　Molecular imprinting of L-glutamine was carried out by using phase-inversion of Nylon-6 in the presence of L-glutamine template. The recognition of L-glutamine analogues by the molecularly imprinted-Nylon-6 was compared and presented. The recognition ability for L-glutamine by imprinted Nylon-6 was high, comparing with the binding efficiency for similar molecules, D-glutamine, L-glutamic acid, and D-glutamic acid. Evidence was indicated by FT-IR analysis that 3450 cm-1 correspond to free amide group, which indicates that the hydrogen-bonding interactions in the imprinted-Nylon-6 was responsible in the high recognition of the amino acid molecules. The equilibrium constants were calculated from the saturation binding curves according to Scatchard plots. The imprinted-Nylon-6 were resulted high recognition with equilibrium constant （KE） = 4.9 x 10^5 M-1 and total number of imprint sites （［IS］total）= 3.9 μmol/g for the template, L-glutamine. The recognition of amino acids by molecularly imprinted Nylon-6 membranes was also investigated in ultrafiltration permeation experiments and observed that the L-glutamine imprinted membrane has highest recognition to the template as compared with its analogues. Similar experiments were carried out to imprint L-phenylalanine （L-PhA） in Nylon-6. The recognition of mixture of L- and D-PhA by the L-PhA-imprinted-Nylon-6 was studied in ultrafiltration permeation. The selectivity for L-PhA by the imprinted Nylon-6 was high, comparing with the binding efficiency for similar molecules, D-PhA. The results obtained indicated that, specific amino acid molecule can be recognized by the membrane in a mixture of molecules.
　Dibenzofuran （DBF） imprinted polymers were prepared with polysulfone （PSf）, polyvinyl chloride （PVC）, polystyrene （PSt）, and polyacrylonitrile （PAN） by phase- inversion method; subsequent extraction of the template molecule with methanol allowed polymers to carry imprint pockets. In this case, FT-IR spectral data have provided information about possible polymer-template interations present in these polymes by observing the difference in spectra of imprinted and template extracted polymers. The recognition experiments of template DBF, and substrates, dibenzo-p-dioxin （DBDO）, dipehnyl ether （DPE）, and 1,4-benzodioxane （BDO） by DBF imprinted polymers were showed that these polymers have recognition ability for template and substrates having similar structures corresponding to the template. Nature of the polymer is a dramatic effect on the recognition process, namely, PVC and PSf showed high binding ability, and the PAN binding was observed to be lowest among the four imprinted polymers examined here. The equilibrium constants for imprinted polymers are higher than that of unimprinted polymers. Also, the recognition properties was widely influenced by solvent medium. The higher selectivities were obtained in methanol medium by the imprinted-polymers. However, the highest binding capacities were achieved in water medium. In case of mixture of equal ratios of methanol-water medium, the obtained selectivities are improved with better binding capacities. Both the binding capacity and selectivity depends strongly on the solvent used in binding studies, where the binding capacity increased with increase of solvent polarity. Some of DBF-imprinted copolymers were also studied for their recognition towards DBF analogues. The present study of substrate recognition shows that the recognition could be achieved for not only template, but also substrates having similar size and shape to those of template. The results were obtained in the investigation gave an idea that it is possible to apply molecularly imprinted polymers to the development of selective recognition materials for environmentally toxic substances, i.e., dioxins. The recognition for similar substrate to such a toxic materials is ideally suited for the separation using imprinted polymers, where such template having toxicity is some times not readily available and not feasible to use in imprinted polymer preparation.
　Diamine-amic acids were synthesized by reacting aromatic diamines with 3,3',4,4'-benzophenonetetracarboxiclic dianhydride in dimethylacetaide （DMAc） and were characterized by melting points, elemental analysis, IR, 1H-NMR, and HPLC. Poly（amide-amic acid）s was prepared by low temperature solution polycondensation of diamine amic acids with isophthaloyl chloride in DMAc. Poly（amide-imide）s with alternative （amide-amide） and （imide-imide） sequences were obtained by cycloimidization of poly（amide-amic acid）s with trietylamine-acetic anhydride （Et3N-Ac2O） mixture in DMAc solution. They were characterized by solubilities, inherent viscosities, IR, and 1H-NMR, and were readily soluble in aprotic solvents such as DMAc, DMF, DMSO, and NMP. Thermal properties of the polymers were measured by differential scanning calorimetry, and thermo gravimetric analysis.