Fluorescence Sensing and Selective Binding of a Novel 4,4′‐Sulfonyldianiline‐Bridged Bis(β‐cyclodextrin) for Bile Salts

A novel 4,4′‐sulfonyldianiline‐bridged bis(β‐cyclodextrin (CD)) 2 was synthesized, and its complex stability constants (K_s) for the 1 : 1 inclusion complexation with bile salts, i.e., cholate (CA), deoxycholate (DCA), glycocholate (GCA), and taurocholate (TCA) have been determined in phosphate buffer (pH 7.2) at 25° by fluorescence spectroscopy. The result indicated that 2 can act as efficient fluorescent sensor and display remarkable fluorescence enhancement upon addition of optically inert bile salts. Structures of the inclusion complexes between bile salts and 2 were elucidated by 2D‐NMR experiments, indicating that the anionic tail group and the D ring of bile salts penetrate into one CD cavity of 2 from the wide opening deeply, while the phenyl moiety of the CD linker is partially self‐included in the other CD cavity to form a host–linker–guest binding mode. As compared with native β‐CD 1 upon complexation with bile salts, bis(β‐CD) 2 enhances the binding ability and molecular selectivity. Typically, 2 gives the highest K_s value of 26200 M ^?1 for the complexation with CA, which may be ascribed to the simultaneous contributions of hydrophobic, H‐bond, and electrostatic interactions. These phenomena are discussed from the viewpoints of multiple recognition and induce‐fit interactions between host and guest.     

1H NMR studies of binary and ternary dapsone supramolecular complexes with different drug carriers: EPC liposome,SBE‐β‐CD and β‐CD

Binary and ternary systems composed of dapsone, sulfobutylether‐β‐cyclodextrin (SBE‐β‐CD), β‐CD and egg phosphatidylcholine (EPC) were evaluated using 1D ROESY, saturation transfer difference NMR and diffusion experiments (DOSY) revealing the binary complexes Dap/β‐CD (K_a 1396 l mol^?1), Dap/SBE‐β‐CD (K_a 246 l mol^?1), Dap/EPC (K_a 84 l mol^?1) and the ternary complex Dap/β‐CD/EPC (K_a 18 l mol^?1) in which dapsone is more soluble. Copyright © 2014 John Wiley & Sons, Ltd.     

Quantitative ROESY analysis of computational models: structural studies of citalopram and β‐cyclodextrin complexes by 1H‐NMR and computational methods

Complexation of racemic citalopram with β‐cyclodextrin (β‐CD) in aqueous medium was investigated to determine atom‐accurate structure of the inclusion complexes. ¹H‐NMR chemical shift change data of β‐CD cavity protons in the presence of citalopram confirmed the formation of 1 : 1 inclusion complexes. ROESY spectrum confirmed the presence of aromatic ring in the β‐CD cavity but whether one of the two or both rings was not clear. Molecular mechanics and molecular dynamic calculations showed the entry of fluoro‐ring from wider side of β‐CD cavity as the most favored mode of inclusion. Minimum energy computational models were analyzed for their accuracy in atomic coordinates by comparison of calculated and experimental intermolecular ROESY peak intensities, which were not found in agreement. Several least energy computational models were refined and analyzed till calculated and experimental intensities were compatible. The results demonstrate that computational models of CD complexes need to be analyzed for atom‐accuracy and quantitative ROESY analysis is a promising method. Moreover, the study also validates that the quantitative use of ROESY is feasible even with longer mixing times if peak intensity ratios instead of absolute intensities are used. Copyright © 2015 John Wiley & Sons, Ltd.     

Veronicafolin－β-环糊精的物化表征及Veronicafolin－羟丙基-β-环糊精包合物溶解性的增强

用氢谱、红外光谱、X-射线粉末衍射、热分析、元素分析等测试方法研究了Veronicafolin (3,5,4′-三羟基-6,7,3′-三甲氧基黄酮) 和β-环糊精 (β-CD) 的固体包合物的谱学特征。元素分析结果显示形成Veronicafolin-β-CD·20H2O包合物，其中C：39.58%, H: 5.75%，表明包合物中主客体比为1∶1。该包合类型属于A_L-型。通过紫外-可见分光光度法研究了在羟丙基-β-环糊精（HP-β-CD）的存在下Veronicafolin的相溶解度曲线，测得校正曲线为y = 24148x + 0.0075 (r=0.9999)，相溶解曲线为y=0.4738x-2.0×10^-7 (r=0.9490)，包结平衡常数Ks为4.5×10⁶mol-1。HP-β-CD提高了黄酮醇Veronicafolin的溶解度。     

Synthesis and Structure of Low‐valent η4‐Cinnamaldehyde Cobalt Complexes

Three η⁴‐(C=C–C=O) coordination cobalt(I) complexes 1 – 3 were synthesized by the reactions of cinnamaldehyde, p‐fluorocinnamaldehyde, and p‐chlorocinnamaldehyde with CoMe(PMe₃)₄. Complex 4 as η²‐(C=C) coordination was prepared by the reaction of chalcone with Co(PMe₃)₄. The structures of complexes 1 – 4 were confirmed by single‐crystal X‐ray diffraction. Although the reactions didn't undergo C–H bond activation and decarbonylation, the formation of complexes 1 – 4 deepens our understanding of the reactions between α,β‐unsaturated aldehyde or ketone with low‐valent central cobalt atom.     

Synthesis and Structural Characterization of ZnII α‐Diimine Complexes with Chloride and Thiocyanate Co‐Ligands

The preparation and spectroscopic and structural characterization of three Zn^II complexes with bis[N‐(2,6‐dimethylphenyl)imine]acenaphthene, L¹, and with bis[N‐(2‐ethylphenyl)imine]acenaphthene, L², are decribed herein. Two of the complexes were prepared from ZnCl₂ and the third from Zn(NCS)₂. One‐pot reaction techniques were used, leading to high yields. The complexes were characterized by microanalysis, IR and ¹H NMR spectroscopy, and single‐crystal X‐ray diffraction. The structures of the complexes are significantly different, with the chloride‐containing species forming distorted tetrahedra around the metal, whereas its thiocyanate analog is dimeric, with each metal at the center of a distorted square pyramid, with bridging and terminal [SCN]^– ligands.     

γ‐Cyclodextrin as Inhibitor of the Precipitation Reaction between Berberine and Glycyrrhizin in Decoctions of Natural Medicines: Interaction Studies of Cyclodextrins with Glycyrrhizin and Glycyrrhetic Acid by 1H‐NMR Spectroscopy and Molecular‐Dynamics Calculation

To prevent the precipitation reaction between glycyrrhizin ( 1 ) and berberine ( 3 ) in the decoctions of Glycyrrhiza/Coptis rhizome or Glycyrrhiza/Phellodendron bark, the presence of cyclodextrin (CD) in the mixture was proven to be effective. The preventing effect decreased in the order γ‐CD>β‐CD, and no effect was observed for α‐CD. On the other hand, the extraction degree of 1 from the natural medicine Glycyrrhia was considerably increased in the presence of γ‐CD, γ‐CD being much more effective than α‐ or β‐CD. Thus, the blocking effect of CD on the precipitate formation between 1 and 3 is suggested to be primarily dependent on the stability of the inclusion complex of the CD with 1 . To establish the structure of such a preferred inclusion complex, the interactions of 1 with β‐ and γ‐CDs were investigated by ¹H‐NMR spectroscopy and molecular‐dynamics (MD) calculations. The ¹H‐NMR measurements showed that the increase in solubility of 1 in H₂O is dependent on the degree of its inclusion into the CD, which depends on the molecular size of the CD. The MD calculations suggested that the H‐bond interactions are sufficiently strong to form a stable [ 1 /γ‐CD] complex, in which the lipophilic rings C, D, and E of 1 are fully inserted into the molecular cavity of γ‐CD, thus forming a kind of structure covered by a hydrophilic molecular capsule, while such an interaction mode is impossible for α‐ or β‐CD.     

Synthesen und Strukturen von Bis(4,4′‐t‐butyl‐2,2′‐bipyridin)‐Ruthenium(II)‐Komplexen mit funktionellen Derivaten des Tetramethyl‐bibenzimidazols

Syntheses and Structures of Bis(4,4′‐t‐butyl‐2,2′‐bipyridine) Ruthenium(II) Complexes with functional Derivatives of Tetramethyl‐bibenzimidazole [(tbbpy)₂RuCl₂] reacts with dinitro‐tetramethylbibenzimidazole ( A ) in DMF to form the complex [(tbbpy)₂Ru( A )](PF₆)₂ ( 1a ) (tbbpy: bis(4,4′‐t‐butyl)‐2,2′bipyridine). Exchange of the two PF₆^? anions by a mixture of tetrafluor‐terephthalat/tetrafluor‐terephthalic acid results in the formation of 1b in which an extended hydrogen‐bonded network is formed. According to the ¹H NMR spectra and X‐ray analyses of both 1a and 1b , the two nitro groups of the bibenzimidazole ligand are situated at the periphery of the complex in cis position to each other. Reduction of the nitro groups in 1a with SnCl₂/HCl results in the corresponding diamino complex 2 which is a useful starting product for further functionalization reactions. Substitution of the two amino groups in 2 by bromide or iodide via Sandmeyer reaction results in the crystalline complexes [(tbbpy)₂Ru( C )](PF₆)₂ and [(tbbpy)₂Ru( D )](PF₆)₂ ( C : dibromo‐tetrabibenzimidazole, D : diiodo‐tetrabibenzimidazole). Furthermore, 2 readily reacts with 4‐t‐butyl‐salicylaldehyde or pyridine‐2‐carbaldehyde under formation of the corresponding Schiff base Ru^II complexes 5 and 6 . ¹H NMR spectra show that the substituents (NH₂, Br, I, azomethines) in 2 ‐ 6 are also situated in peripheral positions, cis to each other. The solid state structure of both 2 , and 3 , determined by X‐ray analyses confirm this structure. In addition, the X‐ray diffraction analyses of single crystals of the complexes [(tri‐t‐butyl‐terpy)(Cl)Ru( A )] ( 7 ) and [( A )PtCl₂] ( 8 ) display also that the nitro groups in these complexes are in a cis‐arrangement.     

Morphological change of poly (ε‐caprolactone) with a wide range of molecular weight via formation of inclusion complex with α‐cyclodextrin

The effect of molecular weight of poly(ε‐caprolactone) (PCL) on the formation and stability of inclusion complexes (ICs) between α‐cyclodextrin (α‐CD) and PCL was investigated by FTIR, WAXD, and DSC measurements. ICs between α‐CD and PCLs with a wide range of number‐average molecular weight, M_n = 1.21 × 10⁴ – 1.79 × 10⁵, were prepared by mixing the aqueous solution of CD and acetone solution of PCL followed by stirring at 60 °C for 1h and at the room temperature for 1 day. FTIR, WAXD, and DSC measurement showed the PCL chains were included into the α‐CD cavity, and the crystallization of PCL was suppressed in the α‐CD cavity. Stoichiometry and yield of each IC varied with the molecular weight of guest PCL, and the effect of IC formation on the crystallization behaviour of guest polymer decreased with the increase of molecular weight of guest polymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1433–1440, 2005     

Stability constants of adducts of succinate copper(II) complexes with β‐cyclodextrin determined by capillary electrophoresis

Cyclodextrins (CD) form inclusion complexes with different “guests” owing to the fact that the shape of the CD molecule is a truncated cone with a hydrophobic cavity. The adducts of CD with metal complexes remain scantily explored. In this study, the stability constants of the adducts between succinate copper(II) complexes and β‐CD was determined using capillary electrophoresis. The β‐CD concentration in background electrolytes (BGE) was found to influence on the effective electrophoretic mobility of the copper(II) complexes in succinate BGEs. It was shown that succinic acid and its anions and copper(II) ions did not form a significant amount of the inclusion complexes with β‐CD and the mobility change was caused by the adduct formation between succinate copper(II) complexes and β‐CD. The stability constants of these adducts were determined at 25°С and ionic strength of 0.100 M: log β(CuL₂²⁻/β‐CD) = 1.76 ± 0.06, log β(CuL⁰/β‐CD) = 0.98 ± 0.09. The [CuHL]⁺ and [CuHL₂]⁻ species were found to do not form adducts with β‐CD.     

Mono‐ and Binuclear Rhodium and Platinum Complexes of 1, 3, 5‐Trimethyl‐1, 3, 5‐triaza‐2σ3λ3‐phosphorin‐4, 6‐dionyloxy‐substituted Calix[4]arenes

The reaction behaviour of 1, 3, 5‐triaza‐2σ³λ³‐phosphorin‐4, 6‐dionyloxy‐substituted calix[4]arenes towards mono‐ and binuclear rhodium and platinum complexes was investigated. Special attention was directed to structure and dynamic behaviour of the products in solution and in the solid state. Depending on the molar ratio of the reactands, the reaction of the tetrakis(triazaphosphorindionyloxy)‐substituted calix[4]arene ( 4 ) and its tert‐butyl‐derivative ( 1 ) with [(cod)RhCl]₂ yielded the mono‐ and disubstituted binuclear rhodium complexes 2 , 3 , and 5 . In all cases, a C₂‐symmetrical structure was proved in solution, apparently caused by a fast intramolecular exchange process between cone conformation and 1, 3‐alternating conformation. The X‐ray crystal structure determination of 5 confirmed [(calixarene)RhCl]₂‐coordination through two opposite phosphorus atoms with a P ⃜P separation of 345 pm. The complex displays crystallographic inversion symmetry, and the Rh₂Cl₂ core is thus exactly planar. Reaction of 1 and of the bis(triazaphosphorindionyloxy)‐bis(methoxy)‐substituted tert‐butyl‐calix‐[4]arene ( 7 ) with (cod)Rh(acac) in equimolar ratio and subsequent reaction with HBF₄ led to the expected cationic monorhodium complexes 5 and 8 , involving 1, 3‐alternating P‐Rh‐P‐coordination. The cone conformation in solution was proved by NMR spectroscopy and characteristic values of the ¹J(PRh) coupling constants in the ³¹P‐NMR‐spectra. Reaction of equimolar amounts of 4 with (cod)Rh(acac) or (nbd)Rh(acac) led, by substitution of the labile coordinated acetylacetonato and after addition of HBF₄, to the corresponding mononuclear cationic complexes 9 and 10 . Only two of the four phosphorus atoms in 9 and 10 are coordinated to the central metal atom. Displacement of either cycloocta‐1, 5‐diene or norbornadiene was not observed. For both compounds, the cone conformation was proved by NMR spectroscopy. Reaction of 4 with (cod)PtCl₂ led to the PtCl₂‐complex ( 11 ). As for all compounds mentioned above, only two phosphorus atoms of the ligand coordinate to platinum, while two phosphorus atoms remain uncoordinated (proved by δ³¹P and characteristic values of ¹J(PPt)). NMR‐spectroscopic evidence was found for the existence of the cone conformation in the cis‐configuration of 11 .     

Discriminating Influence of α‐ and Methylated β‐Cyclodextrins on Complexation and Polymerization of Diacrylate and Dimethacrylate Monomers

Summary: Host‐guest complexes of α‐cyclodextrin (α‐CD) and methylated β‐cyclodextrin (Me‐β‐CD) with diacrylates and dimethacrylates of butan‐1,4‐diol and hexan‐1,6‐diol at varying stoichiometries were studied. The complexes were analyzed by means of ¹H NMR, two‐dimensional ROESY spectroscopy and Job's curves, which clearly revealed the discriminating influence of the two hosts towards complex formation. The corresponding polymers were obtained using a redox initiator system in water. Thermal analysis and IR measurements of the polymers provided evidence for the existence of a polyrotaxane architecture.

Proposed structure of the cross‐linked polymers obtained by the redox polymerization of the Me‐β‐CD complexed monomers.     

Structural Studies for Specific Binding Capacity of β‐Cyclodextrin with Ibuprofen

Ibuprofen (Ibu) and β‐cyclodextrin (βCD) and its derivative (hydroxypropyl‐β‐cyclodextrin, HPβCD) complexes spatial geometry information were studyed. Firstly, phase solubility experiment was carried out for S‐(+)‐ibuprofen (SIbu) and cyclodextrins complex. The apparent stability constant (Kc) for 1:1 complexes are 1065 M‐1 (βCD) and 1476 M‐1 (HPβCD) respectively. Secondly, ¹H NMR and two‐dimensional rotating‐frame overhauser effect spectroscopy (2D ROESY) were used for binding study, and confirmed that benzene ring of Ibu is deeply included into the cavity and racemic Ibu (RSIbu) can be discriminated by βCD or HPβCD. Finally, docking model was given by theoretical investigation. The model with ‐4.77 kcal/mol binding energy matches experimental structure.     

Synthesis and High‐Resolution NMR Structure of a β3‐Octapeptide with and without a Tether Introduced by Olefin Metathesis

Bridging between (i)‐ and (i+3)‐positions in a β³‐peptide with a tether of appropriate length is expected to prevent the corresponding 3₁₄‐helix from unfolding (Fig. 1). The β³‐peptide H‐β³hVal‐β³hLys‐β³hSer(All)‐β³hPhe‐β³hGlu‐β³hSer(All)‐β³hTyr‐β³hIle‐OH ( 1 ; with allylated βhSer residues in 3‐ and 6‐position), and three tethered β‐peptides 2 – 4 (related to 1 through ring‐closing metathesis) have been synthesized (solid‐phase coupling, Fmoc strategy, on chlorotrityl resin; Scheme). A comparative CD analysis of the tethered β‐peptide 4 and its non‐tethered analogue 1 suggests that helical propensity is significantly enhanced (threefold CD intensity) by a (CH₂)₄ linker between the β³hSer side chains (Fig. 2). This conclusion is based on the premise that the intensity of the negative Cotton effect near 215 nm in the CD spectra of β³‐peptides represents a measure of ‘helical content’. An NMR analysis in CD₃OH of the two β³‐octapeptide derivatives without (i.e., 1 ) and with tether (i.e., 4 ; Tables 1–6, and Figs. 4 and 5) provided structures of a degree of precision (by including the complete set of side chain–side chain and side chain–backbone NOEs) which is unrivaled in β‐peptide NMR‐solution‐structure determination. Comparison of the two structures (Fig. 5) reveals small differences in side‐chain arrangements (separate bundles of the ten lowest‐energy structures of 1 and 4 , Fig. 5, A and B ) with little deviation between the two backbones (superposition of all structures of 1 and 4 , Fig. 5, C ). Thus, the incorporation of a CH₂? O? (CH₂)₄? O? CH₂ linker between the backbone of the β³‐amino acids in 3‐ and 6‐position (as in 4 ) does accurately constrain the peptide into a 3₁₄‐helix. The NMR analysis, however, does not suggest an increase in the population of a 3₁₄‐helical backbone conformation by this linkage. Possible reasons for the discrepancy between the conclusion from the CD spectra and from the NMR analysis are discussed.     

Synthesis and Self‐Organization of Zinc β‐(Dialkoxyphosphoryl)porphyrins in the Solid State and in Solution

The first synthesis and self‐organization of zinc β‐phosphorylporphyrins in the solid state and in solution are reported. β‐Dialkoxyphosphoryl‐5,10,15,20‐tetraphenylporphyrins and their Zn^II complexes have been synthesized in good yields by using Pd‐ and Cu‐mediated carbon–phosphorous bond‐forming reactions. The Cu‐mediated reaction allowed to prepare the mono‐β‐(dialkoxyphosphoryl)porphyrins 1 Zn – 3 Zn starting from the β‐bromo‐substituted zinc porphyrinate ZnTPPBr (TPP=tetraphenylporphyrin) and dialkyl phosphites HP(O)(OR)₂ (R=Et, iPr, nBu). The derivatives 1 Zn – 3 Zn were obtained in good yields by using one to three equivalents of CuI. When the reaction was carried out in the presence of catalytic amounts of palladium complexes in toluene, the desired zinc derivative 1 Zn was obtained in up to 72 % yield. The use of a Pd‐catalyzed C? P bond‐forming reaction was further extended to the synthesis of β‐poly(dialkoxyphosphoryl)porphyrins. An unprecedented one‐pot sequence involving consecutive reduction and phosphorylation of H₂TPPBr₄ led to the formation of a mixture of the 2,12‐ and 2,13‐bis(dialkoxy)phosphorylporphyrins 5 H₂ and 6 H₂ in 81 % total yield. According to the X‐ray diffraction studies, 1 Zn and 3 Zn are partially overlapped cofacial dimers formed through the coordination of two Zn centers by two phosphoryl groups belonging to the adjacent molecules. The equilibrium between the monomeric and the dimeric species exists in solutions of 1 Zn and 3 Zn in weakly polar solvents according to spectroscopic data (UV/Vis absorption and NMR spectroscopy). The ratio of each form is dependent on the concentration, temperature, and traces of water or methanol. These features demonstrated that zinc β‐phosphorylporphyrins can be regarded as new model compounds for the weakly coupled chlorophyll pair in the photosynthesis process.     

Functionalized 3,3′,5,5′‐Tetraaryl‐1,1′‐Biphenyls: Novel Platforms for Molecular Receptors

This paper describes the development of novel aromatic platforms for supramolecular construction. By the Suzuki cross‐coupling protocol, a variety of functionalized m‐terphenyl derivatives were prepared (Schemes 1–4). Macrolactamization of bis(ammonium salt) (S,S)‐ 6 with bis(acyl halide) 7 afforded the macrocyclic receptor (S,S)‐ 2 (Scheme 1), which was shown by ¹H‐NMR titration studies to form ‘nesting' complexes of moderate stability (K_a between 130 and 290 M ^?1, 300 K) with octyl glucosides 13 – 15 (Fig. 2) in the noncompetitive solvent CDCl₃. Suzuki cross‐coupling starting from 3,3′,5,5′‐tetrabromo‐1,1′‐biphenyl provided access to a novel series of extended aromatic platforms (Scheme 5) for cleft‐type (Fig. 1) and macrotricyclic receptors such as (S,S,S,S)‐ 1 . Although mass‐spectral evidence for the formation of (S,S,S,S)‐ 1 by macrolactamization between the two functionalized 3,3′,5,5′‐tetraaryl‐1,1′‐biphenyl derivatives (S,S)‐ 33 and 36 was obtained, the ¹H‐ and ¹³C‐NMR spectra of purified material remained rather inconclusive with respect to both purity and constitution. The versatile access to the novel, differentially functionalized 3,3′,5,5′‐tetrabromo‐1,1′‐biphenyl platforms should ensure their wide use in future supramolecular construction.     

New single isomer negatively charged β‐cyclodextrin derivatives as chiral selectors in capillary electrophoresis

To improve resolution power of chiral selector and enantiomeric peak efficiency in CE, single isomer negatively charged β‐CD derivatives, mono(6‐deoxy‐6‐sulfoethylthio)‐β‐CD (SET‐β‐CD) bearing one negative charge and mono[6‐deoxy‐6‐(6‐sulfooxy‐5,5‐bis‐sulfooxymethyl)hexylthio]‐β‐CD (SMHT‐β‐CD) carrying three negative charges, were synthesized. The structure of these two β‐CD derivatives was confirmed by ¹H NMR and MS. SET‐β‐CD and SMHT‐β‐CD successfully resolved the enantiomers of several basic model compounds. SMHT‐β‐CD provided for a significantly greater enantioseparation than SET‐β‐CD at lower concentrations. This appears to be due to the higher binding affinity of SMHT‐β‐CD to the model compounds and the wider separation window resulting from an increased countercurrent mobility of the selector. Overall, the new chiral selectors provided enantioseparations with high peak efficiency while avoiding peak distortion due to polydispersive and electrodispersive effects. The information obtained from an apparent binding constant study suggested that the enantioseparation of the model compounds followed the predictions of charged resolving agent migration model and that the observed degree of enantioseparation difference were due to the magnitude of differences in both enantiomer‐chiral selector binding affinities (ΔK) and the mobilities of the complexed enantiomers (Δμ_c).     

Supramolecular inclusion complexes of a star polymer containing cholesterol end‐capped poly(ε‐caprolactone) arms with β‐cyclodextrin

A novel hexa‐armed and star‐shaped polymer containing cholesterol end‐capped poly(ε‐caprolactone) arms emanating from a phosphazene core (N₃P₃‐(PCL‐Chol)₆) was synthesized by a combination of ring‐opening polymerization and “click” chemistry techniques. For this purpose, the terminal ? OH groups of the synthesized precursor (N₃P₃‐(PCL‐OH)₆) were converted into –Chol through a series of reaction. Both N₃P₃‐(PCL‐OH)₆ and N₃P₃‐(PCL‐Chol)₆ were then employed in the preparation of supramolecular inclusion complexes (ICs) with β‐cyclodextrin (β‐CD). The latter formed ICs with β‐CD in higher yield. The host–guest stoichiometry (ε‐CL:β‐CD, mol:mol) in the ICs of N₃P₃‐(PCL‐Chol)₆ was found to be 1.2. The formation of supramolecular ICs of N₃P₃‐(PCL‐Chol)₆ with β‐CD was confirmed by using Fourier transform infrared (FTIR) and ¹H nuclear magnetic resonance (NMR) spectroscopic methods, wide‐angle X‐ray diffraction (WAXD), and thermal analysis techniques. WAXD data showed that the obtained ICs with N₃P₃‐(PCL‐Chol)₆ had a channel‐type crystalline structure, indicating the suppression of the original crystallization of N₃P₃‐(PCL‐Chol)₆ in β‐CD cavities. Moreover, the thermal stabilities of ICs were found to be higher than those of the free star polymer and β‐CD. Furthermore, the surface properties of N₃P₃‐(PCL‐Chol)₆ and its ICs with β‐CD were investigated by static contact angle measurements. The obtained results proved that the wettability of N₃P₃‐(PCL‐Chol)₆ successfully increased with the formation of its ICs with β‐CD. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3406–3420     

Inclusion of Ethyl Acetoacetate Bearing 7‐Hydroxycoumarin Dye by β‐Cyclodextrin and its Cooperative Assembly with Mercury(II) Ions: Spectroscopic and Molecular Modeling Studies

The inclusion of the fluorescent organic dye, ethyl 3‐(7‐hydroxy‐2‐oxo‐2H‐chromen‐3‐yl)‐3‐oxopropanoate ( 1 ) by the host β‐cyclodextrin (β‐CD), and its response toward mercuric ions (Hg²⁺), was studied by UV/Vis, fluorescence, and ¹H NMR spectroscopic analyses, mass spectrometry and molecular modeling studies. ¹H NMR measurements together with molecular modeling studies for dye 1 demonstrate that it exhibits two tautomeric forms (keto and enol); however, when the dye is included into the β‐CD cavity, the enol form predominates. Moreover, by using spectroscopic and spectrometry techniques, a 1:1 stoichiometry was determined for the complexes formed between dye 1 (enol form) and β‐CD, with a binding constant (K_b1=1.8×10⁴ m ^?1) and for the dye 1 (keto form)‐Hg²⁺ (K_b2=2.3×10³ m ^?1). Interestingly, in the presence of 1 –β‐CD complex and mercuric ions, a ternary supramolecular system (Hg– 1 –β‐CD complex) was established, with a 1:1:1 stoichiometry and a K_b3 value of 4.3×10³ m ^?1, with the keto form of the dye being the only one present in this assembly. The three‐component system provides a starting point for the development of novel and directed supramolecular assemblies.     

High Resolution NMR Spectroscopic Study of Complexation of Hydroxyzine Hydrochloride with β‐Cyclodextrin in Aqueous Solution

Hydroxyzine hydrochloride forms two 1:1 inclusion complexes with β‐cyclodextrin in aqueous solution as confirmed by the ¹H NMR titration and ROESY studies. One complex is formed by the deep penetration of the chlorophenyl ring from the wider rim side, while the mode of entry of the phenyl ring into the β‐CD cavity is not clear. The stoichiometry and overall association constant of the complexes have been determined by the treatment of ¹H NMR shift data. Some chiral discrimination by the host between the two enantiomers of hydroxyzine hydrochloride is also indicated.