Well-defined AB 3 -type miktoarm star-shaped polymers with cholic acid (CA) core were fabricated with a combination of "click" chemistry and ring opening polymerization (ROP) methods. Firstly, azide end-functional poly(ethylene glycol) (mPEG), poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(e-caprolactone) (PCL) polymers were prepared via controlled polymerization and chemical modification methods. Then, CA moieties containing three OH groups were introduced to these polymers as the end groups via Cu(I)-catalyzed click reaction between azide end-functional groups of the polymers (mPEG-N 3 , PMMA-N 3 , PS-N 3 , and PCL-N 3 ) and ethynylfunctional CA under ambient conditions, yielding CA endfunctional polymers (mPEG-Cholic, PMMA-Cholic, PS-Cholic, and PCL-Cholic). Finally, the obtained CA end-capped polymers were employed as the macroinitiators in the ROP of e-caprolactone (e-CL) yielding AB 3 -type miktoarm star polymers (mPEG-Cholic-PCL 3 , PMMA-Cholic-PCL 3 , and PS-Cholic-PCL 3 ) and asymmetric star polymer [Cholic-(PCL) 4 ]. The chemical structures of the obtained intermediates and polymers were confirmed via Fourier transform infrared and 1 H nuclear magnetic resonance spectroscopic techniques. Thermal decomposition behaviors and phase transitions were studied in detail using thermogravimetric analysis and differential scanning calorimetry experiments.
An efficient stereospecific synthesis of the plant hormone ( RS)-abscisic acid from the readily available 4-oxoisophorone, trimethylsilylacetylene and ethyl but-2-ynoate, is described.
A novel hexa-armed and star-shaped polymer containing cholesterol end-capped poly(e-caprolactone) arms emanating from a phosphazene core (N 3 P 3 -(PCL-Chol) 6 ) was synthesized by a combination of ring-opening polymerization and "click" chemistry techniques. For this purpose, the terminal AOH groups of the synthesized precursor (N 3 P 3 -(PCL-OH) 6 ) were converted into -Chol through a series of reaction. Both N 3 P 3 -(PCL-OH) 6 and N 3 P 3 -(PCL-Chol) 6 were then employed in the preparation of supramolecular inclusion complexes (ICs) with b-cyclodextrin (b-CD). The latter formed ICs with b-CD in higher yield. The host-guest stoichiometry (e-CL:b-CD, mol:mol) in the ICs of N 3 P 3 -(PCL-Chol) 6 was found to be 1.2. The formation of supramolecular ICs of N 3 P 3 -(PCL-Chol) 6 with b-CD was confirmed by using Fourier transform infrared (FTIR) and 1 H nuclear magnetic resonance (NMR) spectroscopic methods, wide-angle X-ray diffraction (WAXD), and thermal analysis techniques. WAXD data showed that the obtained ICs with N 3 P 3 -(PCL-Chol) 6 had a channel-type crystalline structure, indicating the suppression of the original crystallization of N 3 P 3 -(PCL-Chol) 6 in b-CD cavities. Moreover, the thermal stabilities of ICs were found to be higher than those of the free star polymer and b-CD. Furthermore, the surface properties of N 3 P 3 -(PCL-Chol) 6 and its ICs with b-CD were investigated by static contact angle measurements. The obtained results proved that the wettability of N 3 P 3 -(PCL-Chol) 6 successfully increased with the formation of its ICs with b-CD. V C 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3406-3420
A comparison between the -and -facial selectivity observed in the hydroboration of some androst-5-enes and B-norandrost-5-enes does not parallel the difference between the calculated force field energies for -and -cyclobutane models suggesting that the facial selectivity is not determined by the four-centre transition state but by the relative ease of formation of the initial %-complex between the alkene and the borane.
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