Synthesis,purification, and characterization of “perfect” star polymers via “Click” coupling

The copper (I)‐catalyzed azide‐alkyne cycloaddition “click” reaction was successfully applied to prepare well‐defined 3, 6, and 12‐arms polystyrene and polyethylene glycol stars. This study focused particularly on making “perfect” star polymers with an exact number of arms, as well as developing techniques for their purification. Various methods of characterization confirmed the star polymers high purity, and the structural uniformity of the generated star polymers. In particular, matrix‐assisted laser desorption ionization‐time‐of‐flight mass spectrometry revealed the quantitative transformation of the end groups on the linear polymer precursors and confirmed their quantitative coupling to the dendritic cores to yield star polymers with an exact number of arms. In addition to preparing well‐defined polystyrene and poly(ethylene glycol)homopolymer stars, this technique was also successfully applied to amphiphilic, PCL‐b‐PEG star polymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Hyperbranched cyclic and multicyclic polymers by “a2+b4” polycondensations

At first, theoretical aspects of “a₂+b₄” polycondensations (meaning polycondensations of difunctional and tetrafunctional monomers) are discussed and compared with what is known about “a₂+b₃” polycondensations. The following review of experimental results is subdivided into three sections. First, syntheses of hyperbranched polyethers and polyesters by polycondensations based on equimolar feed ratios will be reported. Second, kinetically controlled (i.e., irreversible) syntheses of multicyclic polymers using equifunctional feed ratios (i.e., a₂/b₄ ratios of 2:1) will be described. In the third section, syntheses of multicyclic polymers via thermodynamically controlled (reversible) “a₂+b₄” polycondensations will be discussed. Characteristic for these polycondensations are again equifunctional feed ratios and metal alkoxides as “a₂” or “b₄” monomers, which catalyze rapid equilibration reactions. Finally, potential applications of the new polymers will shortly be mentioned. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1971–1987, 2009     

The Correct Meaning of “Coating Efficiency” vs. the “Utilization of Theoretical Efficiency”

The correct meaning of the the term “utilization of the theoretical efficiency” vs. the “coating efficiency” is explained.     

A Quantitative Assessment of „Through-space”︁ and „Through-bond”︁ Interactions. Application to Semi-empirical SCF Models

The scheme of ‘through-space’ and ‘through-bond’ interaction of (semi)localized orbitals, originally proposed by Hoffmann, is reexamined in terms of SCF many-electron treatments. It is shown that the two types of interaction can be characterized by examining the corresponding off-diagonal matrix elements of the Hartree-Fock matrices of the localized or the symmetry adapted localized orbitals and of the partially diagonalized Hartree-Fock matrices referring to ‘precanonical orbitals’. The procedure outlined is applied to three practical examples using the semiempirical many-electron treatments SPINDO, MINDO/2 and CNDO/2:

• a A reassessment of ‘through-space’ and ‘through-bond’ interaction in norbornadiene indicates, that the latter type of interaction is also of importance for the orbital based mainly on the antisymmetric combination of the localized x-orbitals. The differences in the predictions derived from the three models are critically examined.
• b The competition between ‘through-space’ and ‘through-bond’ interaction in the series of bicyclic dienes from norbornadiene to bicyclo[4.2.2]-dcca-7,9-diene and in cyclohexa-1,4-diene, i. e. their dependence on the dihedral angle UI is reexamined. It is found that the rationalization for the orbital crossing near ω = 130° deduccd from PE. spectroscopic data can not be as simple as originally suggested and that the relay’ orbitals responsible for ‘through-bond interaction affecting both the symmetric and the antisymmetric combination of the π-orbitals extend over the whole CC-σ-system of the six membered ring.
• c ‘Through-bond’ interaction of the two lone pair orbitals in 1,4-diazabicyclo[2.2.2]octane is found to be large for their symmetric and the antisymmetric linear combination.

The analysis quoted, draws attention to some of the dangers involved in using semiempirical treatments for the interpretation of PE. data in terms of Koopmans′ theorem, without due caution.     

Transformation of “living” carbocationic and other polymerizations to controlled/“living” radical polymerization

Transformation of “living” carbocationic polymerization of styrene and isobutene to controlled atom transfer radical polymerization (ATRP) is described and formation of the corresponding AB and ABA block copolymers with styrene (St), methyl methacrylate (MMA, methyl acrylate (MA) and isobornyl acrylate (IBA) was demonstrated. A similar approach was applied to the cationic ring opening polymerization of tetrahydrofuran leading to the AB and ABA block copolymers with St, MMA and MA using ATRP. Site transformation approach was also used for the ring opening metathesis polymerization of norbornene and polycondensation systems using polysulfone as an example. In both cases, AB and ABA block copolymers were efficiently formed with styrene and acrylates.     

A new method for “ferrous iron” and “excess oxygen” in rocks, minerals, and oxides

A new method is given whereby oxygen excess or deficiency in many minerals and oxides may be simply determined. The method depends on the stability in phosphoric acid-pyrophosphate mixtures of both Mn^III and Mn^II. The sample is dissolved in a phosphoric acid mixture containing excess Mn^II, with or without the addition of standard oxidant, and Mn^III remaining in solution or produced by reaction with the sample is titrated with ferrous ammonium sulphate, using barium diphenylamine sulphate as indicator. The method is useful in many cases where existing methods are inapplicable or unsatisfactory. Accurate results can be obtained using relatively small samples.