Lanthanide chelates containing pyridine units with potential application as contrast agents in magnetic resonance imaging

A new pyridine-containing ligand, N,N'-bis(6-carboxy-2-pyridylmethyl)ethylenediamine-N,N'-diacetic acid (H(4)L), has been designed for the complexation of lanthanide ions. (1)H and (13)C NMR studies in D(2)O solutions show octadentate binding of the ligand to the Ln(III) ions through the nitrogen atoms of two amine groups, the oxygen atoms of four carboxylates, and the two nitrogen atoms of the pyridine rings. Luminescence measurements demonstrate that both Eu(III) and Tb(III) complexes are nine-coordinate, whereby a water molecule completes the Ln(III) coordination sphere. Ligand L can sensitize both the Eu(III) and Tb(III) luminescence; however, the quantum yields of the Eu(III)- and Tb(III)-centered luminescence remain modest. This is explained in terms of energy differences between the singlet and triplet states on the one hand, and between the 0-phonon transition of the triplet state and the excited metal ion states on the other. The anionic [Ln(L)(H2O)]- complexes (Ln=La, Pr, and Gd) were also characterized by theoretical calculations both in vacuo and in aqueous solution (PCM model) at the HF level by means of the 3-21G* basis set for the ligand atoms and a 46+4 f(n) effective core potential for the lanthanides. The structures obtained from these theoretical calculations are in very good agreement with the experimental solution structures, as demonstrated by paramagnetic NMR measurements (lanthanide-induced shifts and relaxation-rate enhancements). Data sets obtained from variable-temperature (17)O NMR at 7.05 T and variable-temperature (1)H nuclear magnetic relaxation dispersion (NMRD) on the Gd(III) complex were fitted simultaneously to give insight into the parameters that govern the water (1)H relaxivity. The water exchange rate (k(298)(ex)=5.0 x 10(6) s(-1)) is slightly faster than in [Gd(dota)(H2O)]- (DOTA=1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane). Fast rotation limits the relaxivity under the usual MRI conditions.     

Paenilamicin: Structure and Biosynthesis of a Hybrid Nonribosomal Peptide/Polyketide Antibiotic from the Bee Pathogen Paenibacillus larvae

The spore‐forming bacterium Paenibacillus larvae is the causative agent of American Foulbrood (AFB), a fatal disease of honey bees that occurs worldwide. Previously, we identified a complex hybrid nonribosomal peptide/polyketide synthesis (NRPS/PKS) gene cluster in the genome of P. larvae. Herein, we present the isolation and structure elucidation of the antibacterial and antifungal products of this gene cluster, termed paenilamicins. The unique structures of the paenilamicins give deep insight into the underlying complex hybrid NRPS/PKS biosynthetic machinery. Bee larval co‐infection assays reveal that the paenilamicins are employed by P. larvae in fighting ecological niche competitors and are not directly involved in killing the bee larvae. Their antibacterial and antifungal activities qualify the paenilamicins as attractive candidates for drug development.     

Synthesis of Levulinic Acids From Muconic Acids in Hot Water

Levulinic acid is a key biorenewable platform molecule. Its current chemical production from sugars is plagued by limited yields, char formation and difficult separations. An alternative and selective route starting from muconic acid via simple heating in water at high temperature (180 °C) has been developed. Muconic acid can be obtained from sugars or catechol fermentation. Chemical oxidation of catechol is another possibility which advantageously can also be applied on substituted catechols, hereby providing substituted muconic acids. When applying the disclosed hydrothermal protocol on these substrates hitherto unknown substituted levulinic acids were accessed. In particular, 3-propyllevulinic acid has been synthesized from 4-propylcatechol, prepared from pine wood. This propylated derivative has been used for the synthesis of a 3-propyllevulinate diester, i.e. butane-1,4-diyl bis(4-oxo-3-propylpentanoate), via esterification with 1,4-butanediol. The diester showed superior performance as plasticizer in comparison to the corresponding levulinate diester in both PVC (polyvinyl chloride) and PLA (polylactic acid). It plasticizes equally effective as the notorious commercial phthalate-based benchmark DEHP (di-2-ethylhexyl phthalate) in PVC.     

Subcoercivity and subelliptic operators on Lie groups I: Free nilpotent groups

Let (χ, G, U) be a continuous representation of a Lie groupG by bounded operatorsg →U(g) on the Banach space χ and let (χ, $\mathfrak{g}$ ,dU) denote the representation of the Lie algebra $\mathfrak{g}$ obtained by differentiation. Ifa ₁, ...,a _d′ is a Lie algebra basis of $\mathfrak{g}$ ,A _i=dU(a _i) and $A^\alpha = A_{i_1 } ...A_{i_k } $ whenever α=(i ₁, ...,i _k) we consider the operators $$H = \mathop \sum \limits_{\alpha ;|\alpha | \leqslant 2n} c_\alpha A^\alpha $$ where thec _α are complex coefficients satisfying a subcoercivity condition. This condition is such that the class of operators considered encompasses all the standard second-order subelliptic operators with real coefficients, all operators of the form $\sum _{i = 1}^{d'} \lambda _i ( - A_i^2 )^n $ with Re λ _i >0 together with operators of the form $$H = ( - 1)^n \mathop \sum \limits_{\alpha ;|\alpha | = n} \mathop \sum \limits_{\beta ;|\beta | = n} c_{\alpha ,\beta } A^{\alpha _* } A^\beta $$ where α_*=(i _k, ...,i ₁) if α=(i ₁, ...,i _k) and the real part of the matrix (c _{α β}) is strictly positive. In case the Lie algebra $\mathfrak{g}$ is free of stepr, wherer is the rank of the algebraic basisa ₁, ...,a _d′,G is connected andU is the left regular representation inG we prove that the closure $\overline H $ ofH generates a holomorphic semigroupS. Moreover, the semigroupS has a smooth kernel and we derive bounds on the kernel and all its derivatives. This will be a key ingredient for the paper [13] in which the above results will be extended to general groups and representations.     

Generalized Multiresolution Analyses with Given Multiplicity Functions

Generalized multiresolution analyses are increasing sequences of subspaces of a Hilbert space ℋ that fail to be multiresolution analyses in the sense of wavelet theory because the core subspace does not have an orthonormal basis generated by a fixed scaling function. Previous authors have studied a multiplicity function m which, loosely speaking, measures the failure of the GMRA to be an MRA. When the Hilbert space ℋ is L ²(ℝ ⁿ ), the possible multiplicity functions have been characterized by Baggett and Merrill. Here we start with a function m satisfying a consistency condition, which is known to be necessary, and build a GMRA in an abstract Hilbert space with multiplicity function m.     

Zeros of linear combinations of Laguerre polynomials from different sequences

We study interlacing properties of the zeros of two types of linear combinations of Laguerre polynomials with different parameters, namely and . Proofs and numerical counterexamples are given in situations where the zeros of R_n, and S_n, respectively, interlace (or do not in general) with the zeros of , , k=n or n−1. The results we prove hold for continuous, as well as integral, shifts of the parameter α.     

The construction of wavelets from generalized conjugate mirror filters in

The classical constructions of wavelets and scaling functions from conjugate mirror filters are extended to settings that lack multiresolution analyses. Using analogues of the classical filter conditions, generalized mirror filters are defined in the context of a generalized notion of multiresolution analysis. Scaling functions are constructed from these filters using an infinite matrix product. From these scaling functions, non-MRA wavelets are built, including one whose Fourier transform is infinitely differentiable on an arbitrarily large interval.