Macrocyclic Chemistry: New Research Developments

MACROCYCLIC CHEMISTRY:  NEW RESEARCH DEVELOPMENTS......Page 8
CONTENTS......Page 10
PREFACE......Page 12
ABSTRACT......Page 20
1. INTRODUCTION - AZACROWNS AS MULTIPURPOSE LIGANDS OR RECEPTORS (STRUCTURAL ASPECTS)......Page 21
2. NMR SPECTROSCOPY OF TETRAAZACYCLOTETRADECANES AND STRUCTURALLY SIMILAR POLYAZA MACRORINGS......Page 26
2.1. NMR Measurements for Polyamines in Aqueous Solutions (General Remarks)......Page 28
2.2. Determining Protonation Mechanisms Through NMR pH-Titration Spectroscopy......Page 34
2.2.1. Amino protonation-induced changes in δXs......Page 35
2.2.2. Use of empirical ‘shielding constants’......Page 36
2.2.4. Similarity of pH-titration profiles (1H and 13C NMR spectra)......Page 38
2.2.5. 13C NMR line-broadening effects......Page 39
2.3. pH-Driven Internal Dynamics in Azacrowns as Probed by the 13C T1 Rates [83]......Page 40
2.4. Polyamine 3 in the Strongly Acidic Medium: a Rejection of the Working Proposal of an Active Participation of the Nitrate Anion [85]......Page 41
3. COMPUTATIONAL METHODS FOR AZACROWN MACROCYCLES AND RELATED POLYPROTONATED SPECIES......Page 43
3.1. MMX vs. OPLS-AA Force Field (Creation of Initial Molecular Models)......Page 44
3.2. Overall Conformations of the Macrocycles Forced by Their Dynamics......Page 46
3.3. Empirically Corrected (Linearly Scaled) DFT GIAO-based Predictions of δXs for Aqueous Solutions......Page 52
3.4. Behind a ‘Free-Molecule’ Approach......Page 54
4. POLYAZA AND OTHER MACROCYCLES - SOME CURRENT ACHIEVEMENTS......Page 56
5. CONCLUSION......Page 61
REFERENCES......Page 62
ABSTRACT......Page 70
INTRODUCTION......Page 71
Crystal Structures of Calixarene Complexes......Page 73
Concurrent Insertion of Solvent Molecules in Solutions......Page 74
Gas-Phase Interactions of Calixarenes with Molecular Guests......Page 76
Adsorption of Organic Vapors within Calixarene Thin Films......Page 86
Molecular Recognition of Organic Guest Vapors by Solid Calixarenes......Page 88
Transport of Small Mobile Particles Through a Calixarene Crystal......Page 93
REFERENCES......Page 97
ABSTRACT......Page 106
1. INTRODUCTION......Page 107
2. AN APPROXIMATE EVALUATION OF POSSIBLE INFLUENCE FACTORS ON THE INTERMOLECULAR INTERACTIONS BETWEEN CDS AND GUESTS......Page 108
3. A CAREFUL COMPARISON OF THE INCLUSION INTERACTIONS BETWEEN CDS AND A SERIES OF ANALOGUES......Page 112
4. REPRESENTATIVE INCLUSION SYSTEMS IN LEVEL D......Page 121
5. REPRESENTATIVE INCLUSION SYSTEMS IN LEVEL C......Page 122
6. REPRESENTATIVE INCLUSION SYSTEMS IN LEVEL B......Page 125
7. REPRESENTATIVE INCLUSION SYSTEMS IN LEVEL A......Page 131
8. THE DISCRIMINATION BEHAVIOR OF THE  SAME GUEST TO A GROUP CDS......Page 134
9. SEVERAL EXAMPLES OF CD INCLUSION COMPLEXES WITH STOICHIOMETRIES OTHER THAN 1:1......Page 138
10. SEVERAL EXAMPLES ON THE APPLICATION OF MOLECULAR DISCRIMINATION PHENOMENA OF CDS TO A GROUP OF  GUESTS IN MODERN CHEMISTRY......Page 139
11. CONCLUSION......Page 140
REFERENCES......Page 141
1. INTRODUCTION......Page 148
2.2. The Glycopeptide Antibiotics......Page 150
3.2. Separation on Teicoplanin and Teicoplanin-Related CSPS......Page 156
3.3. Separation on Ristocetin a CSP......Page 160
3.4. Separation on Vancomycin and Vancomycin Analog CSPs......Page 161
3.5. Parallel Application of Macrocyclic Glycopeptide CSPs and Comparison of their Separation Efficiencies......Page 163
4. MECHANISTIC CONSIDERATIONS......Page 164
5. ELUTION SEQUENCE AND ABSOLUTE CONFIGURATION......Page 170
REFERENCES......Page 171
ABSTRACT......Page 178
1. INTRODUCTION......Page 179
2. POLY-AZA-MACROCYCLIC SYSTEMS......Page 182
2.1. Sensing Effects......Page 191
2.3. Nucleotide Recognition......Page 196
3. OXA-AZA MACROCYCLES......Page 198
4. THIA-AZA MACROCYCLES......Page 207
5. OTHER MACROCYCLE LIGANDS......Page 219
6. CONCLUSIONS......Page 224
REFERENCES......Page 225
ABSTRACT......Page 232
INTRODUCTION......Page 233
1. POLYSACCHARIDES AS METAL IONS COLLECTORS......Page 234
1.1. Numeric Calculations......Page 235
2.1. Rheological Studies of Starch Complexes with Metal Salts......Page 237
3.1. Biofuels from Cereal Grains/Metal Complexes......Page 238
3.1.1. Carbonizate production from cereal grains/metal complexes......Page 239
3.1.2. Syngas production from cereal grains......Page 240
3.2. Biofuels from Polysaccharide Starches......Page 242
4. SOIL STABILIZATION BY POLYSACCHARIDES......Page 244
REFERENCES......Page 245
INTRODUCTION......Page 252
STRUCTURE OF CYCLODEXTRINS......Page 253
Relief of Conformational Strain......Page 255
Hydrogen Bonding......Page 256
Hydrophobic Interactions......Page 257
STOICHIOMETRY AND BINDING CONSTANT DETERMINATION......Page 258
UV-Vis Spectroscopy......Page 259
Fluorescence Spectroscopy......Page 260
NMR Spectroscopy......Page 261
Microcalorimetric Titration......Page 262
BINDING OF AMINO ACIDS BY CYCLODEXTRINS......Page 263
INTERACTIONS OF SMALL PEPTIDES WITH CYCLODEXTRINS......Page 276
INTERACTIONS OF CDS WITH POLYPEPTIDES AND PROTEINS......Page 277
REFERENCES......Page 278
ABSTRACT......Page 282
INTRODUCTION......Page 283
RESULTS AND DISCUSSION......Page 284
Complex Formation with α-CD......Page 285
Complex Formation with β-CD......Page 292
Complex Formation with Modified β-CDs......Page 298
REFERENCES......Page 301
ABSTRACT......Page 306
1. INTRODUCTION......Page 307
2.1. Reagents......Page 309
2.2. Sample Preparation......Page 310
2.4. NMR Data treatment, complex formation constants evaluation......Page 311
3. RESULTS AND DISCUSSION......Page 313
REFERENCES......Page 321
ABSTRACT......Page 326
INTRODUCTION......Page 327
ION SOLVATION EFFECTS......Page 328
USE OF PROTON-IONIZABLE MACROCYCLES......Page 329
TRANSPORT BULK LIQUID MEMBRANE......Page 330
METAL ION TRANSPORT ACROSS SUPPORTED LIQUID MEMBRANE......Page 331
Bulk Liquid Membrane (BLM)......Page 333
Polymer Inclusion Membrane (PIM)......Page 334
LIQUID-LIQUID EXTRACTION......Page 335
EXPERIMENTAL REMARKS......Page 337
REFERENCES......Page 342
INTRODUCTİON......Page 344
AMINES AND AMINO ALCOHOLS......Page 345
AMINO ACID DERIVATIVES AND PEPTIDES......Page 348
FLUORESCENT GROUPS......Page 357
SUGARS......Page 360
TARTARIC ACID DERIVATIVES......Page 363
CİNCHONA ALKALOİDS......Page 364
CAMPHOR SULFONYL CHLORIDE......Page 365
EPOXIDES AND GLYCIDYL GROUPS......Page 367
CYCLODEXTRINS......Page 368
GUANIDINIUM SALTS......Page 369
Miscellaneous......Page 370
REFERENCES......Page 376
ABSTRACT......Page 382
1. INTRODUCTION......Page 383
2.1. O-Functionalization Phenolic Fragments of Resorc[4]arenes......Page 384
2.2. C-N(S)- Functionalization of Phenolic Fragments of Resorcin[4]arenes......Page 391
3. SYNTHESIS OF RESORCINARENES MODIFIED AT THE NARROW RIM OF THE MOLECULE......Page 394
4. APPLICATIONS......Page 395
REFERENCES......Page 408
1. INTRODUCTION......Page 412
2. SYNTHESIS OF IMINE MACROCYCLES......Page 414
3. SYNTHESIS OF TRIPHENYLAMINE-BASED IMINE MACROCYCLES......Page 418
3.1. Characterization of Imine Macrocycles......Page 420
4. SYNTHESIS OF TRIPHENYLAMINE-BASED POLYRHOMBIMINES......Page 427
REFERENCES......Page 432
INTRODUCTION......Page 436
THE RECOGNITION BY CRYPTANDS AND PROTONATED CRYPTANDS......Page 437
THE RECOGNITION BY CRYPTATES......Page 443
THE ACTIVATION BY POLYAZA MACROCYCLIC LIGANDS AND THEIR COMPLEXES......Page 446
REFERENCES......Page 449
ABSTRACT......Page 454
INTRODUCTION......Page 455
2. Methods......Page 457
1. Phase Solubility Behavior......Page 459
2. Rose-Drago Method......Page 460
3. In Vitro Antifungal Activity Studies......Page 461
CONCLUSION......Page 463
REFERENCES......Page 464
ABSTRACT......Page 466
1. INTRODUCTION......Page 467
2.1. The 1H-NMR Experiment......Page 468
2.1.1. Stoichiometry of inclusion compounds......Page 469
2.1.2. Apparent inclusion constants of inclusion compounds......Page 470
2.1.3. Complexation thermodynamics of β-CD.CGA......Page 471
2.2. The Raman Experiment......Page 472
2.2.1. The Raman experiment shows that inclusion also occurs in solid state......Page 473
2.3. Model Calculations Study......Page 474
CONCLUSION......Page 476
REFERENCES......Page 477
ABSTRACT......Page 478
1. INTRODUCTION......Page 479
2.2.1. Small scale bioassay......Page 481
3.1. Potato Storage Experiments......Page 482
3.2. Chemical Analyses and Sensory Evaluation of Chips......Page 484
4. CONCLUSION......Page 485
REFERENCES......Page 486
1. INTRODUCTION......Page 488
2. UREA AS AN ADDUCTOR......Page 493
3.4 Non-linear optics......Page 497
UREA CO-INCLUSION COMPOUNDS......Page 498
 5.1 Infrared Spectroscopy......Page 502
5.3 Polycrystalline X-Ray Diffraction......Page 503
6.1 Improvement in dissolution profile of drugs......Page 504
6.3 Improved chemical stability......Page 506
6.4 Improved moisture stability......Page 507
6.6 Conversion of liquid drug into solid......Page 508
CONCLUSION......Page 509
REFERENCES......Page 510
INDEX......Page 518