Poly(N-vinylimidazole/ethylene glycol dimethacrylate) for the purification and isolation of phenolic acids

In this study we report the novel polymeric resin poly(N-vinyl imidazole/ethylene glycol dimethacrylate) for the purification and isolation of phenolic acids. The monomer to crosslinker ratio and the porogen composition were optimized for isolating phenolic acids diluted in acetonitrile at normal phase chromatography conditions, first. Acetonitrile serves as polar, aprotic solvent, dissolving phenolic acids but not interrupting interactions with the stationary phase due to the approved Hansen solubility parameters. The optimized resin demonstrated high loading capacities and adsorption abilities particularly for phenolic acids in both, acetonitrile and aqueous solutions. The adsorption behavior of aqueous standards can be attributed to ion exchange effects due to electrostatic interactions between protonated imidazole residues and deprotonated phenolic acids. Furthermore, adsorption experiments and subsequent curve fittings provide information of maximum loading capacities of single standards according to the Langmuir adsorption model. Recovery studies of the optimized polymer in the normal-phase and ion-exchange mode illustrate the powerful isolation properties for phenolic acids and are comparable or even better than typical, commercially available solid phase extraction materials. In order to prove the applicability, a highly complex extract of rosemary leaves was purified by poly(N-vinyl imidazole/ethylene glycol dimethacrylate) and the isolated compounds were identified using UHPLC–qTOF-MS.     

Spin-state dynamics of a photochromic iron(II) complex and its immobilization on oxide surfaces via phenol anchors

This work presents a detailed study of the photo-induced spin-state dynamics of the photochromic iron(II) complex 1, where the metal ion is in the field of a tripodal hexa-imine ligand with protolysable phenol groups. The nature of the complex’s ground state has been identified as a spin singlet by ¹H NMR and steady-state UV/vis spectroscopies, and its distorted octahedral structure was analyzed via crystal structure determination. Sub-picosecond and nanosecond time-resolved laser flash photolysis experiments identify the long-lived quintet state of 1 as the selective product of photoexcitation in the UV/vis spectral region. Thermal barriers of spin-state interconversion as a function of solvent and added base are derived from temperature-dependent rates of transient decay. Ground-state recovery is found to be significantly affected by the solvent and is strongly enhanced, in particular, by base-driven solvolysis of the ligand’s phenol groups. Partial spontaneous deprotonation of the phenolic hydroxyl groups of 1 seems to prevail on metal oxide surfaces, i.e. on alumina. Composite materials, like 1 at Al₂O₃, that retain the characteristic spectral features of the parent iron(II) complex can be readily obtained by wet impregnation of hydrous alumina with solutions of 1.     

Multistep energy and electron transfer processes in novel rotaxane donor–acceptor hybrids generating microsecond-lived charge separated states

A new set of [Cu(phen)₂]⁺ based rotaxanes, featuring [60]-fullerene as an electron acceptor and a variety of electron donating moieties, namely zinc porphyrin (ZnP), zinc phthalocyanine (ZnPc) and ferrocene (Fc), has been synthesized and fully characterized with respect to electrochemical and photophysical properties. The assembly of the rotaxanes has been achieved using a slight variation of our previously reported synthetic strategy that combines the Cu(i)-catalyzed azide–alkyne cycloaddition reaction (the “click” or CuAAC reaction) with Sauvage''s metal-template protocol. To underline our results, complementary model rotaxanes and catenanes have been prepared using the same strategy and their electrochemistry and photo-induced processes have been investigated. Insights into excited state interactions have been afforded from steady state and time resolved emission spectroscopy as well as transient absorption spectroscopy. It has been found that photo-excitation of the present rotaxanes triggers a cascade of multi-step energy and electron transfer events that ultimately leads to remarkably long-lived charge separated states featuring one-electron reduced C₆₀ radical anion (C₆₀˙^–) and either one-electron oxidized porphyrin (ZnP˙⁺) or one-electron oxidized ferrocene (Fc˙⁺) with lifetimes up to 61 microseconds. In addition, shorter-lived charge separated states involving one-electron oxidized copper complexes ([Cu(phen)₂]²⁺ (τ < 100 ns)), one-electron oxidized zinc phthalocyanine (ZnPc˙⁺; τ = 380–560 ns), or ZnP˙⁺ (τ = 2.3–8.4 μs), and C₆₀˙^– have been identified as intermediates during the sequence. Detailed energy diagrams illustrate the sequence and rate constants of the photophysical events occurring with the mechanically-linked chromophores. This work pioneers the exploration of mechanically-linked systems as platforms to position three distinct chromophores, which are able to absorb light over a very wide range of the visible region, triggering a cascade of short-range energy and electron transfer processes to afford long-lived charge separated states.     

What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a?/w or d/z? ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS³ experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π–π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer.

Open image in new window

Graphical Abstract

     

Distributional Transformations Without Orthogonality Relations

Distributional transformations characterized by equations relating expectations of test functions weighted by a given biasing function on the original distribution to expectations of the test function’s higher derivatives with respect to the transformed distribution play a great role in Stein’s method and were, in great generality, first considered by Goldstein and Reinert (J Theoret Probab 18(1):237–260, 2005. doi: 10.1007/s10959-004-2602-6). We prove two abstract existence and uniqueness results for such distributional transformations, generalizing their \(X-P\)-bias transformation. On the one hand, we show how one can abandon previously necessary orthogonality relations by subtracting an explicitly known polynomial depending on the test function from the test function itself. On the other hand, we prove that for a given nonnegative integer m, it is possible to obtain the expectation of the m-th derivative of the test function with respect to the transformed distribution in the defining equation, even though the biasing function may have \(k<m\) sign changes, if these two numbers have the same parity. We explain how these results can be used to guarantee the existence of two different generalizations of the zero-bias transformation by Goldstein and Reinert (Ann Appl Probab 7(4):935–952, 1997. doi: 10.1214/aoap/1043862419). Further applications include the derivation of Stein-type characterizations without needing to solve any Stein equation and the presentation of a general framework for estimating the distance from the distribution of a given real random variable X to that of a random variable Z, whose distribution is characterized by some mth-order linear differential operator. We also explain the fact that, in general, the biased distribution depends on the choice of the sign change points, if these are ambiguous. This new phenomenon does not appear in the framework from Goldstein and Reinert (2005).     

On Eigenvalues of the Transition Matrix of Some Count-Data Markov Chains

We analyze the eigenstructure of count-data Markov chains. Our main focus is on so-called CLAR(1) models, which are characterized by having a linear conditional mean, and also on the case of a finite range, where the second largest eigenvalue determines the speed of convergence of the forecasting distributions. We derive a lower bound for the second largest eigenvalue, which often (but not always) even equals this eigenvalue. This becomes clear by deriving the complete set of eigenvalues for several specific cases of CLAR(1) models.     

Band-dominated operators on metric measure spaces

We generalise the notion of band-dominated operators originally introduced for the space ℓ_p(ℤⁿ) to the setup of metric measure spaces and show various algebraic properties of this space of operators. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)