Predictions of pulsed field gradient NMR echo-decays for molecules diffusing in various restrictive geometries. Simulations of diffusion propagators based on a finite element method

Pulsed field gradient NMR diffusometry is a promising tool for investigating structures of porous material through determinations of dynamic displacements of molecules in porous systems. A problem with this approach is the lack of closed analytical expressions for echo-decays in anything but idealized pore geometries. We present here an approach based on calculating the appropriate diffusion propagator by means of finite element calculations. The suggested method is quite general, and can be applied to arbitrary porous systems. The protocol for the calculations is outlined and we show results from some different cases: diffusion in confined geometries and in systems that are spatially inhomogeneous with respect to concentration.     

Hyperpolarization of 13C through order transfer from parahydrogen: a new contrast agent for MRI

The order within proton pairs in organic molecules, resulting from hydrogenation with parahydrogen, can be transferred in great part to nearby carbon 13 spins through adequate field manipulations. The molecules with hyperpolarized 13C thus obtained can be used as new contrast agents of high efficiency in MRI. After a brief presentation of the hydrogenation process and apparatus, in relatively low magnetic field, we describe the procedure of order transfer to the 13C spins through a sudden drop from the initial field to zero field followed by an adiabatic remagnetization. The expected final polarizations in the absence of relaxation are given for several compounds. Finally, we show an example of MR images observed in vivo on animals as an illustration of the contrast capacity of this new method.     

Determination of organophosphate esters in air samples by dynamic sonication-assisted solvent extraction coupled on-line with large-volume injection gas chromatography utilizing a programmed-temperature vaporizer

An on-line method for the determination of airborne organophosphate esters based on dynamic sonication-assisted solvent extraction and large-volume injection (LVI) gas chromatography with nitrogen-phosphorous detection is introduced. The LVI is performed with a programmed-temperature vaporizer. The entire extracted fraction of 800 microl (hexane-methyl-tert.-butyl ether, 7:3, v/v) is introduced directly into the GC system without any clean-up step following extraction. The extraction and analysis step were completed in less than 15 min. The limit of detection of the investigated organophosphate esters was established to be in the range of 5-32 pg/filter. The correlation coefficients (r2) were investigated in the linear range study of the entire system and established to be approximately 0.9900 for all the investigated organophosphates esters. Applications of the method was demonstrated with the extraction of air samples collected onto glass fiber filters from different indoor environments. Six organophosphate esters were found at the levels 0.4-138 ng/m3.     

Unveiling the complex configurational landscape of the intralayer cavities in a crystalline carbon nitride

The in-depth understanding of the reported photoelectrochemical properties of the layered carbon nitride, poly(triazine imide)/LiCl (PTI/LiCl), has been limited by the apparent disorder of the Li/H atoms within its framework. To understand and resolve the current structural ambiguities, an optimized one-step flux synthesis (470 °C, 36 h, LiCl/KCl flux) was used to prepare PTI/LiCl and deuterated-PTI/LiCl in high purity. Its structure was characterized by a combination of neutron/X-ray diffraction and transmission electron microscopy. The range of possible Li/H atomic configurations was enumerated for the first time and, combined with total energy calculations, reveals a more complex energetic landscape than previously considered. Experimental data were fitted against all possible structural models, exhibiting the most consistency with a new orthorhombic model (Sp. Grp. Ama2) that also has the lowest total energy. In addition, a new Cu(i)-containing PTI (PTI/CuCl) was prepared with the more strongly scattering Cu(i) cations in place of Li, and most closely matching with the partially-disorder structure in Cmc2₁. Thus, a complex configurational landscape of PTI is revealed to consist of a number of ordered crystalline structures that are new potential synthetic targets, such as with the use of metal-exchange reactions.

The layered carbon nitride, poly(triazine imide), exhibits a complex configurational landscape for the coordination of cations within its intralayer cavities that has been elucidated for the first time.     

Threshold strangeness production in pp interactions

During the actual lectures, features of the COSY-Jülich accelerator were presented, followed by a short summary of ongoing experiments at the COoler SYnchrotron COSY using internal as well as external beams in the range of 45 MeV to 2.5 GeV. Here the research of the COSY-11 collaboration is presented. This °⁰ facility studies the hidden and open strangeness production observing the ν and η′ as well the K⁺Y and K⁺K^? production in the proton—proton interactions at the respective thresholds.     

Electrochemical and Scalable Dehydrogenative C(sp3)−H Amination via Remote Hydrogen Atom Transfer in Batch and Continuous Flow

A hydrogen atom transfer-directed electrochemical intramolecular C−H amination has been developed in which the N-radical species are generated at the anode, and the base required for the reaction is generated at the cathode. A broad range of valuable pyrrolidines were prepared in good yields and with high chemoselectivity. The reaction was easily scaled up in both batch and continuous flow systems.     

Path coupling without contraction

Path coupling is a useful technique for simplifying the analysis of a coupling of a Markov chain. Rather than defining and analysing the coupling on every pair in Ω×Ω, where Ω is the state space of the Markov chain, analysis is done on a smaller set SΩ×Ω. If the coefficient of contraction β is strictly less than one, no further analysis is needed in order to show rapid mixing. However, if β=1 then analysis (of the variance) is still required for all pairs in Ω×Ω. In this paper we present a new approach which shows rapid mixing in the case β=1 with a further condition which only needs to be checked for pairs in S, greatly simplifying the work involved. We also present a technique applicable when β=1 and our condition is not met.     

Entire functions with Julia sets of positive measure

Let f be a transcendental entire function for which the set of critical and asymptotic values is bounded. The Denjoy–Carleman–Ahlfors theorem implies that if the set of all z for which |f(z)| > R has N components for some R > 0, then the order of f is at least N/2. More precisely, we have log log M(r, f) ≥ (N/2) log r − O(1), where M(r, f) denotes the maximum modulus of f. We show that if f does not grow much faster than this, then the escaping set and the Julia set of f have positive Lebesgue measure. However, as soon as the order of f exceeds N/2, this need not be true. The proof requires a sharpened form of an estimate of Carleman and Tsuji related to the Denjoy–Carleman–Ahlfors theorem.