Comprehensive two-dimensional liquid chromatography for the characterization of functional acrylate polymers

Comprehensive two-dimensional liquid chromatography-size-exclusion chromatography (LC x SEC) was investigated as a tool for the characterization of functional poly(methyl methacrylate) (PMMA) polymers. Ultraviolet-absorbance and evaporative light-scattering detection (ELSD) were used. A simple method to quantify ELSD data is presented. Each data point from the ELSD chromatogram can be converted into a mass concentration using experimental calibration curves. The qualitative and quantitative information obtained on two representative samples is used to demonstrate the applicability of LC x SEC for determining the mutually dependent molar-mass distributions (MMD) and functionality-type distributions (FTD) of functional polymers. The influence of the molar mass on the retention behavior in LC was investigated using LC x SEC for hydroxyl-functional PMMA polymers. The critical conditions, at which retention is--by definition--independent of molar mass, were not exactly the same for PMMA series with different end-groups. Our observations are in close agreement with theoretical curves reported in the literature. However, for practical applications of LC x SEC it is not strictly necessary to work at the exact critical solvent composition. Near-critical conditions are often sufficient to determine the mutually dependent distributions (MMD and FTD) of functional polymers.     

Duplex Stabilization of DNA: Oligonucleotides containing 7-substituted 7-deazaadenines

The oligonucleotide building blocks 4b–d derived from 7-bromo-, 7-chloro-, and 7-methyl-substituted 7-deaza-2′-deoxyadenosines 3b–d were prepared. They were employed in the solid-phase synthesis of the oligonucleotides 7–25 . The dA residues of the homomer d(A₁₂), the alternating d[(A-T)₆], and the palindromic d(G-T-A-G-A-A-T-T-C-T-A-C) were replaced by 3b–d as well as by the parent 7-deaza-2′-deoxyadenosine ( 3a ). The melting profiles and CD spectra of oligonucleotide duplexes, showing this major groove modification, were measured, and the T_m values as well as the thermodynamic data were determined. It was found that small substituents such as Br, Cl, or Me introduced in the 7-position of a 7-deazaadenine residue increase the duplex stability compared to oligonucleotides containing adenine.     

The Wittig Reaction in Industrial Practice

The effects of a scientific discovery on industrial practice are illustrated with reference to the Wittig reaction. The aim of utilizing the Wittig reaction of linking terpenoid building blocks to give vitamin A and carotenoids on an industrial scale prompted extensive research and development work of a synthetic and chemical engineering nature. The importance of the Wittig reaction and its variants in the synthesis of active compounds and fine chemicals in industrial research is demonstrated in the present article.     

Specific labeling of cell surface proteins with chemically diverse compounds

The specific and covalent labeling of fusion proteins with synthetic molecules opens up new ways to study protein function in the living cell. Here we present a novel method that allows for the specific and exclusive extracellular labeling of proteins on the surfaces of live cells with a large variety of synthetic molecules including fluorophores, protein ligands, or quantum dots. The approach is based on the specific labeling of fusion proteins of acyl carrier protein with synthetic molecules through post-translational modification catalyzed by phosphopantetheine transferase. The specificity and versatility of the labeling should allow it to become an important tool for studying and manipulating cell surface proteins and for complementing existing approaches in cell surface engineering.     

On solving a D.C. programming problem by a sequence of linear programs

We are dealing with a numerical method for solving the problem of minimizing a difference of two convex functions (a d.c. function) over a closed convex set in ⁿ . This algorithm combines a new prismatic branch and bound technique with polyhedral outer approximation in such a way that only linear programming problems have to be solved.Parts of this research were accomplished while the third author was visiting the University of Trier, Germany, as a fellow of the Alexander von Humboldt foundation.     

A functional inequality for real-analytic functions

Summary Forf ( C ⁿ() and 0 t x letJ _n (f, t, x) = (–1)ⁿ f(–x)f ⁽ⁿ⁾(t) +f(x)f ⁽ⁿ⁾ (–t). We prove that the only real-analytic functions satisfyingJ _n (f, t, x) 0 for alln = 0, 1, 2, are the exponential functionsf(x) = c e ^x,c, . Further we present a nontrivial class of real-analytic functions satisfying the inequalitiesJ ₀ (f, x, x) 0 and ₀ ^x (x – t)^{n – 1}J_n(f, t, x)dt 0 (n 1).     

Infinitesimal obstructions to weakly mixing

Let ^t be the flow (parametrized with respect to arc length) of a smooth unit vector field v on a closed Riemannian manifold M ⁿ , whose orbits are geodesics. Then the (n-1)-plane field normal to v, v, is invariant under d ^t and, for each x M, we define a smooth real function _x (t) : (1 + _i (t)), where the _i(t) are the eigenvalues of AA ^T, A being the matrix (with respect to orthonormal bases) of the non-singular linear map d^2t , restricted to v at the point _x ^-t M ⁿ.Among other things, we prove the Theorem (Theorem II, below). Assume v is also volume preserving and that _x ^' (t) 0 for all x M and real t; then, if _x ^t : M M is weakly missng for some t, it is necessary that vx 0 at all x M.     

Another remark on twisted convolution

SiaF un gruppo di Lie connesso. Una distribuzioneT a supporto compatto inF e un 2-cociclo diF a valori complessi di modulo 1, definiscono, mediante la convoluzione «twisted», un operatore lineareT _c nello spazio (F). Per il «cociclo triviale»e≡1 l'operatoreT _e è la convoluzione ordinaria. Si dimostra cheT _c permette un'estensione continua suL ^p (F), 1T _e permette una tale estensione. PerF=C _n si ottiene, come caso speciale, un teorema di M. Cowling.     

Microscopic study of a lattice defect trapped at in impurities in plastically deformed Al

¹¹¹In doped Al specimes (c _In1 ppm) were cold worked by extension at 77 K to several amounts of strain. The PAC method was applied to study the trapping of lattice defects at the indium impurities between 77 K and 293 K. From electron irradiation experiments it is known that the In probes are suitable traps for self-interstitials in Al. Since in the present experiment no such effect is observed, it is concluded that by extension at 77 K in Al essentially no freely migrating interstitials are created. Between 110 K and 210 K an increasing fraction of the indium impurities traps a well defined defect. The symmetry axis of the resulting indium-defect-complex is found to point along 111 crystallographic directions. It is proposed that the In impurity traps a divacancy at nearest neighbour sites and relaxes into the open space, thus forming an equilateral triangle of three vacancies in a {111} plane with the In atom in its centre. Reasons for the formation of this complex at rather low annealing temperatures are discussed.