Synthesis,Solid‐State NMR Characterization,and Application for Hydrogenation Reactions of a Novel Wilkinson’s‐Type Immobilized Catalyst

Silica nanoparticles (SiNPs) were chosen as a solid support material for the immobilization of a new Wilkinson’s‐type catalyst. In a first step, polymer molecules (poly(triphenylphosphine)ethylene (PTPPE); 4‐diphenylphosphine styrene as monomer) were grafted onto the silica nanoparticles by surface‐initiated photoinferter‐mediated polymerization (SI‐PIMP). The catalyst was then created by binding rhodium (Rh) to the polymer side chains, with RhCl₃ ? x H₂O as a precursor. The triphenylphosphine units and rhodium as Rh^I provide an environment to form Wilkinson’s catalyst‐like structures. Employing multinuclear (³¹P, ²⁹Si, and ¹³C) solid‐state NMR spectroscopy (SSNMR), the structure of the catalyst bound to the polymer and the intermediates of the grafting reaction have been characterized. Finally, first applications of this catalyst in hydrogenation reactions employing para‐enriched hydrogen gas (PHIP experiments) and an assessment of its leaching properties are presented.     

Level Anti‐Crossings are a Key Factor for Understanding para‐Hydrogen‐Induced Hyperpolarization in SABRE Experiments

Various hyperpolarization methods are able to enhance the sensitivity of nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) by several orders of magnitude. Among these methods are para‐hydrogen‐induced polarization (PHIP) and signal amplification by reversible exchange (SABRE), which exploit the strong nuclear alignment of para‐hydrogen. Several SABRE experiments have been reported but, so far, it has not been possible to account for the experimentally observed sign and magnetic‐field dependence of substrate polarization. Herein, we present an analysis based on level anti‐crossings (LACs), which provides a complete understanding of the SABRE effect. The field‐dependence of both net and anti‐phase polarization is measured for several ligands, which can be reproduced by the theory. The similar SABRE field‐dependence for different ligands is also explained. In general, the LAC concept allows complex spin dynamics to be unraveled, and is crucial for optimizing the performance of novel hyperpolarization methods in NMR and MRI techniques.     

Synthesis and testing of a p-H2 hyperpolarized 13C probe based on the pyrazolo[1,5-a]pyrimidineacetamide DPA-713, an MRI vector to target the peripheral benzodiazepine receptors

DPA-713 is the lead compound of a recently developed 2-phenylpyrazolo[1,5-a]pyrimidineacetamide series that has been shown to display a good targeting capability toward peripheral benzodiazepine receptors, recently renamed translocator protein (18 kDa) or in short TSPO. On the basis of this structure, a novel derivative bearing a [(13)C]butynoate moiety has been designed and synthesized (three steps-42% overall yield) providing, upon rapid and quantitative para-hydrogenation, the corresponding hyperpolarized [(13)C]alkene. Para-hydrogen-induced polarization effects have been detected in both (1)H and (13)C-NMR spectra. Upon applying a field cycling procedure, the spin order of para-H(2) added hydrogens is transferred on the (13)C carboxylate moiety yielding a signal enhancement of approximately 4500 times. T(1) of the carboxylate carbon atom is approximately 21.9 s (at 9.37 T). A (13)C-MR image has been acquired by using the (13)C RARE (Rapid Acquisition by Relaxation Enhancement) acquisition protocol on a 10-mM solution. The main limitation to the in vivo use of this novel para-hydrogenated [(13)C]derivative is its relatively low solubility in aqueous systems.     

Zeros of a family of hypergeometric para‐orthogonal polynomials on the unit circle

Para‐orthogonal polynomials derived from orthogonal polynomials on the unit circle are known to have all their zeros on the unit circle. In this note we study the zeros of a family of hypergeometric para‐orthogonal polynomials. As tools to study these polynomials, we obtain new results which can be considered as extensions of certain classical results associated with three term recurrence relations and differential equations satisfied by orthogonal polynomials on the real line. One of these results which might be considered as an extension of the classical Sturm comparison theorem, enables us to obtain monotonicity with respect to the parameters for the zeros of these para‐orthogonal polynomials. Finally, a monotonicity of the zeros of Meixner‐Pollaczek polynomials is proved.     

Separation of the ortho and para NMR signals in solid deuterium via DQ filtering

Double quantum (DQ) filtering is shown to lead to an effective separation of the NMR signals from the para (I = 1) and ortho (I = 2) molecules in solid deuterium. The separation is achieved by the pulse sequence 90_φ^°–t_pr–90_φ^°–t_ev–90_x^°–t, where the phase-cycled first two pulses create the DQ coherence. Two components are observed after the third pulse; the para signal shows the maximum at a short time t while the ortho signal reaches the maximum at a longer t. The observed signal can be expressed as ∑_I [F_I(t_pr − t) − F_I(t_pr + t)], where F_I(t) is a proper fitting function for the free induction signal of the para and ortho molecules (with I = 1 or 2, respectively). Numerical fits to experimental data at 4.2 and 2 K show that this method can be used to determine the ratio F₁(0)/F₂(0) and thus, because the initial value F_I(0) is proportional to the respective magnetization before the pulse sequence, the ortho and para concentrations in solid deuterium.     

2D NMR Trace Analysis by Continuous Hyperpolarization at High Magnetic Field

Nuclear magnetic resonance is often the technique of choice in chemical analysis because of its sensitivity to molecular structure, quantitative character, and straightforward sample preparation. However, determination of trace analytes in complex mixtures is generally limited by low sensitivity and extensive signal overlap. Here, we present an approach for continuous hyperpolarization at high magnetic field that is based on signal amplification by reversible exchange (SABRE) and can be straightforwardly incorporated in multidimensional NMR experiments. This method was implemented in a 2D correlation experiment that allows detection and quantification of analytes at nanomolar concentration in complex solutions.     

Accessing Remote meta‐ and para‐C(sp2)−H Bonds with Covalently Attached Directing Groups

Directing group assisted ortho‐C?H activation has been known for the last few decades. In contrast, extending the same approach to achieve activation of the distal meta‐ and para‐C?H bonds in aromatic molecules remained elusive for a long time. The main challenge is the conception of a macrocyclic transition state, which is needed to anchor the metal catalyst close to the target bond. Judicious modification of the chain length, the tether linkage, and the nature of the catalyst‐coordinating donor atom has led to a number of successful studies in the last few years. This Review compiles the significant achievements made in this field of both meta‐ and para‐selectivity using covalently attached directing groups, which are systematically classified on the basis of their mode of covalent attachment to the substrate as well as their chemical nature. This Review aims to create a more heuristic approach for recognizing the suitability of the directing groups for use in future organic transformations.     

Meta‐linked and para‐linked water‐soluble poly(arylene ethynylene)s with amino acid side chains: Effects of different linkage on Hg2+ ion sensing properties in aqueous media

Water‐soluble, meta‐ and para‐linked poly(arylene ethynylene)s containing L ‐aspartic acid‐functionalized fluorene units (P1 and P2) and their model compounds (M1 and M2) have been synthesized, and their photophysical properties and fluorescent sensing properties were investigated in aqueous solution. P1 and M1 with the meta‐linkage show blue‐shifted absorption and emission spectra, and decreased photoluminescence quantum yields compared with those of P2 and M2 with para‐linkage. Their absorption and fluorescence spectra are pH dependent perhaps due to the aggregation of the polymer chains at low pH values. In buffer solutions, both polymers and their model compounds exhibit the excellent selectivity and sensitivity to Hg²⁺ over other common metal ions. Furthermore, the quenching constant and detection limit of P1 are determined to be 1.04 × 10⁷ M^?1 and 10 nM, and show the higher sensitivity compared to P2. Further comparison of their model compounds reveal that the sensitivity and quenching efficiency of M1 is also higher than that of M2, indicating that the meta‐linkage pattern plays a key role in improving their Hg²⁺ ion sensing properties. In addition, both meta‐ and para‐linked polymers exhibit the higher quenching efficiency than their model compounds due to the amplified fluorescence response of conjugated polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Experimental and Computational Studies on the Formation of Three para‐Benzyne Analogues in the Gas Phase

Experimental and computational studies on the formation of three gaseous, positively‐charged para‐benzyne analogues in a Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometer are reported. The structures of the cations were examined by isolating them and allowing them to react with various neutral reagents whose reactions with aromatic carbon‐centered σ‐type mono‐ and biradicals are well understood. Cleavage of two iodine–carbon bonds in N‐deuterated 1,4‐diiodoisoquinolinium cation by collision‐activated dissociation (CAD) produced a long‐lived cation that showed nonradical reactivity, which was unexpected for a para‐benzyne. However, the reactivity closely resembles that of an isomeric enediyne, N‐deuterated 2‐ethynylbenzonitrilium cation. A theoretical study on possible rearrangement reactions occurring during CAD revealed that the cation formed upon the first iodine atom loss undergoes ring‐opening before the second iodine atom loss to form an enediyne instead of a para‐benzyne. Similar results were obtained for the 5,8‐didehydroisoquinolinium cation and the 2,5‐didehydropyridinium cation. The findings for the 5,8‐didehydroisoquinolinium cation are in contradiction with an earlier report on this cation. The cation described in the literature was regenerated by using the literature method and demonstrated to be the isomeric 5,7‐didehydro‐isoquinolinium cation and not the expected 5,8‐isomer.