Covalent attachment of poly(ethyleneglycol) to peptides and proteins

Carbonylimidazol-l-yl-mPEG is obtained quantitatively by reacting methoxypoly(ethyleneglycol) (mPEG) with 1.1 Eq of N,N′-carbonyldiimidazole in the presence of a stoechiometric amount of 4-dimethyl-aminopyridine used as hypernucleophilic acylation catalyst. Carbonylimidazol-l-yl-mPEG is quite stable in aqueous solutions with half-lives up to 70 h in pHs ranging from 6.0 to 7.0 at 25‡C. From reactivity studies toward amines with various nucleophilic strengths, it is suggested that carbonylimidazol-l-yl-mPEG may be best used to modify α-amino terminal function of proteins selectively or to introduce amino function on PEG chains.     

Synthesis,kinetic study,and application of Ti[O(CH2)4OCHCH2]4 in ring‐opening polymerization of ε‐caprolactone and radical polymerization

Ti[O(CH₂)₄OCH?CH₂]₄, used for the ring‐opening polymerization (ROP) of ε‐caprolactone, was synthesized through the ester‐exchange reaction of titanium n‐propoxide and 1,4‐butanediol vinyl ether, and its chemical structure was confirmed by nuclear magnetic resonance (¹H NMR) and thermogravimetric analysis (TGA). The mechanism and kinetics of Ti[O(CH₂)₄OCH?CH₂]₄‐initiated bulk polymerization of ε‐caprolactone were investigated. The results demonstrate that Ti[O (CH₂)₄OCH?CH₂]₄‐initiated polymerization of ε‐caprolactone proceeds through the coordination‐insertion mechanism, and all the four alkoxide arms in Ti[O (CH₂)₄OCH?CH₂]₄ share a similar activity in initiating ROP of ε‐caprolactone. The polymerization process can be well predicted by the obtained kinetic parameters, and the activation energy is 106 KJ/mol. Then, the rheological method was employed to investigate the feasibility of producing the crosslinked poly(ε‐caprolactone)‐poly (n‐butyl acrylate) network by using Ti[O(CH₂)₄OCH?CH₂]₄ as the ROP initiator. The tensile test demonstrates that the in situ generated crosslinked PCL‐PBA network in PMMA matrix provides the possibility of ameliorating the tensile properties of PMMA. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7773–7784, 2008     

5-epi-Canadensene and other novel metabolites of Taxus canadensis

The Canadian yew distinguishes itself from other yews by the nature of its taxane metabolites. We are now reporting a new canadensene taxane whose stereochemistry is rigorously established. The three-dimensional structures of canadensene, 5-epi-canadensene and three other related bicyclic taxanes isolated from other yews were calculated using distance constraints derived from NMR data. The stereochemistry of the substituents, the polar acetate groups and the double bonds determine the 3D models. In addition, three new taxanes were also characterized and some biosynthetic speculations are presented.     

Blow up in finite time and dynamics of blow up solutions for the -critical generalized KdV equation

In this paper, we describe the dynamics of blow up solutions for the critical generalized KdV equation such that the initial data is close to the soliton in and has decay in at the right. In particular, we prove that blow up occurs in finite time, and we obtain an upper bound on the blow up rate.

     

A study of the reaction of n-BuLi with Ti(Oi-Pr)4 as a method to generate titanacyclopropane and titanacyclopropene species

The use of the combination of reagents Ti(Oi-Pr)₄/n-BuLi, introduced by the group of J.J. Eisch in 2001, has only found a few applications so far, with sometimes conflicting observations. This article describes a study aimed at clarifying the nature, the stability and the reactivity of the active organometallic species involved. Reactions with CO₂ and other trapping reagents reveal that it is generated within a few minutes at 0 °C in THF, where it can be considered to be stable for 30 min. Most of our results are consistent with the expected titanacyclopropane nature of this reagent but some observations suggest that the chemistry at play may be more complicated.     

The Idempotents of the TL n -Module {\otimes^{n}\mathbb{C}2} in Terms of Elements of {{\rm U}_{q} \mathfrak{sl}_2}

The vector space \({\otimes^{n}\mathbb{C}^2}\) upon which the XXZ Hamiltonian with n spins acts bears the structure of a module over both the Temperley–Lieb algebra \({{\rm TL}_{n}(\beta = q + q^{-1})}\) and the quantum algebra \({{\rm U}_{q} \mathfrak{sl}_2}\) . The decomposition of \({\otimes^{n}\mathbb{C}^2}\) as a \({{\rm U}_{q} \mathfrak{sl}_2}\) -module was first described by Rosso (Commun Math Phys 117:581–593, 1988), Lusztig (Cont Math 82:58–77, 1989) and Pasquier and Saleur (Nucl Phys B 330:523–556, 1990) and that as a TL _n -module by Martin (Int J Mod Phys A 7:645–673, 1992) (see also Read and Saleur Nucl Phys B 777(3):316–351, 2007; Gainutdinov and Vasseur Nucl Phys B 868:223–270, 2013). For q generic, i.e. not a root of unity, the TL _n -module \({\otimes^{n}\mathbb{C}^2}\) is known to be a sum of irreducible modules. We construct the projectors (idempotents of the algebra of endomorphisms of \({\otimes^{n}\mathbb{C}^2}\) ) onto each of these irreducible modules as linear combinations of elements of \({{\rm U}_{q} \mathfrak{sl}_2}\) . When q = q _c is a root of unity, the TL _n -module \({\otimes^{n}\mathbb{C}^2}\) (with n large enough) can be written as a direct sum of indecomposable modules that are not all irreducible. We also give the idempotents projecting onto these indecomposable modules. Their expression now involves some new generators, whose action on \({\otimes^{n}\mathbb{C}^2}\) is that of the divided powers \({(S^{\pm})^{(r)} = \lim_{q \rightarrow q_{c}} (S^{\pm})^r/[r]!}\) .     

On the Gibbs states of the noncritical Potts model on \mathbb Z ^2

We prove that all Gibbs states of the $q$ -state nearest neighbor Potts model on $\mathbb Z ^2$ below the critical temperature are convex combinations of the $q$ pure phases; in particular, they are all translation invariant. To achieve this goal, we consider such models in large finite boxes with arbitrary boundary condition, and prove that the center of the box lies deeply inside a pure phase with high probability. Our estimate of the finite-volume error term is of essentially optimal order, which stems from the Brownian scaling of fluctuating interfaces. The results hold at any supercritical value of the inverse temperature $\beta >\beta _c (q) = \log \left(1+\sqrt{q}\right)$ .