Poly(ethylene terephthalate) copolymers containing nitroterephthalic units. I. Synthesis and characterization

The synthesis, microstructure, and thermal behavior of a series of poly(ethylene terephthalate) (PET) copolymers containing nitroterephthalic units are described. These novel copolyesters were synthesized by transesterification followed by melt copolycondensation of dimethyl terephthalate and dimethyl nitroterephthalate mixtures with ethylene glycol. The molar ratio of the two comonomers in the feed varied from 95/5 to 25/75. Furthermore, PET and poly(ethylene nitroterephthalate) homopolymers were synthesized with the same method and comparatively studied. Copolyester compositions were practically the same as in the feed, and weight‐average molecular weights ranged from 10,000 to 60,000. The two monomeric units were randomly distributed along the polymer chain, and the experimentally determined average sequence lengths were in accordance with ideal copolycondensation statistics. Melting temperatures and enthalpies of the copolyesters decreased with increasing content in nitroterephthalic units, and they all showed a single glass‐transition temperature superior to that of PET. They appeared to be stable up to 300 °C, and thermal degradation occurred in two well‐differentiated steps. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3761–3770, 2000     

A microscopic view of a helical poly(γ‐peptide): Molecular dynamics simulations of a 20‐residue un‐ionized poly(γ‐D‐glutamic acid) in water

We present a molecular dynamics study of the helical conformation of the naturally occurring poly(γ‐D ‐glutamic acid) in the un‐ionized state. The study was conducted in both aqueous solution and gas‐phase considering a 20 residue polypeptide. The results indicated that the left‐handed helix with 19‐membered ring hydrogen bonds set between the CO of the amide group i and the NH of amide group i + 3 is very stable in aqueous solution. This conformation was recently proposed for this poly(γ‐amino acid) from a conformational search study. A detailed picture of the most relevant structural details of the helical conformation of poly(γ‐D ‐glutamic acid) is provided.     

A Proof of Sznitman's Conjecture about Ballistic RWRE

We consider random walk in a uniformly elliptic i.i.d. random environment in ℤ^d for d ≥ 2 . It is believed that whenever the random walk is transient in a given direction it is necessarily ballistic. In order to quantify the gap which would be needed to prove this equivalence, several ballisticity conditions have been introduced. In particular, Sznitman defined the so-called conditions (T) and (T′) . The first one is the requirement that certain unlikely exit probabilities from a set of slabs decay exponentially fast with their width L . The second one is the requirement that for all γ ∈ (0, 1) condition (T)_γ is satisfied, which in turn is defined as the requirement that the decay is like for some C > 0 . In this article we prove a conjecture of Sznitman from 2002, stating that (T) and (T′) are equivalent. Hence, this closes the circle proving the equivalence of conditions (T) , (T′) , and (T)_γ for some γ ∈ (0, 1) as conjectured by Sznitman, and also of each of these ballisticity conditions with the polynomial condition (P)_M for M ≥ 15d + 5 introduced by Berger, Drewitz, and Ramı́rez in 2014. © 2019 Wiley Periodicals, Inc.     

The Gauche Effect in XCH2CH2X Revisited

We have quantum chemically investigated the rotational isomerism of 1,2-dihaloethanes XCH₂CH₂X (X = F, Cl, Br, I) at ZORA-BP86-D3(BJ)/QZ4P. Our Kohn-Sham molecular orbital (KS-MO) analyses reveal that hyperconjugative orbital interactions favor the gauche conformation in all cases (X = F−I), not only for X = F as in the current model of this so-called gauche effect. We show that, instead, it is the interplay of hyperconjugation with Pauli repulsion between lone-pair-type orbitals on the halogen substituents that constitutes the causal mechanism for the gauche effect. Thus, only in the case of the relatively small fluorine atoms, steric Pauli repulsion is too weak to overrule the gauche preference of the hyperconjugative orbital interactions. For the larger halogens, X⋅⋅⋅X steric Pauli repulsion becomes sufficiently destabilizing to shift the energetic preference from gauche to anti, despite the opposite preference of hyperconjugation.     

Synthesis and conjugation of a triiodohydroxylamine for the preparation of highly X‐ray opaque poly(ε‐caprolactone) materials

To address a need for highly X‐ray opaque biodegradable materials, a series of poly(ε‐caprolactone) derivatives were prepared using oxime post‐polymerization modification to conjugate two different iodinated hydroxylamines. These materials were synthesized with up to 32 wt. % iodine content and demonstrated improved X‐ray contrast relative to both the ketone precursors and previously reported monoiodinated materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 787–793     

Factorial design evaluation of the Suzuki cross-coupling reaction using a magnetically recoverable palladium catalyst

A magnetically recoverable catalyst [Fe₃O₄@SiO₂-AEAPTMS-Pd(II)] was prepared, fully characterized and had its catalytic activity evaluated on the Suzuki cross-coupling reaction under microwave irradiation. The reaction conditions for the synthesis of biaryl compounds was optimized in two stages - an initial fractional design 2⁴, in which the parameters reaction time, temperature, solvent and catalyst loading were evaluated, followed by a Doehlert design. The factorial design proved to be a viable approach for obtaining the optimal reaction conditions based on a relatively small number of experiments. Additionally, the biaryl derivatives synthesized by this method were obtained with good to excellent yields (71–96%) and the recovery and reuse of the palladium catalyst was also evaluated.