New C2-Chiral Bidentate Ligands Bridging the gap between donor phosphine and acceptor carbonyl ligands

Two new C₂ chiral bidentate phosphorous ligands have been prepared in enantiomerically pure form. The two phosphorous centers bear electron-withdrawing groups ((CF₃)₂CH? O, C₆F₅) and are linked by a trans-cyclopentane-1,2-diol-derived bridge. Photolysis of [Cr(η⁶-C₆H₆)(CO)₃] in the presence of these two new ligands and of two previously reported bidentate phosphites, and fluorophosphinites (L) afforded [Cr(η⁶-C₆H₆)(CO)L] complexes. IR Spectral comparison of the complexes shows the new ligands to be intermediate in their bonding properties between alkyl phosphites and CO.     

TEMPO‐Mediated Emulsion Polymerization

While miniemulsion polymerization has proven to be well‐suited for conducting living/controlled radical polymerizations, emulsion polymerizations have proven to be far more challenging. Ab initio emulsion polymerizations, in which monomer droplets are present during polymerization, have thus far not been successful with TEMPO‐mediated polymerizations, as a result of colloidal instability and coagulum formation. By selectively inhibiting polymerization in the monomer droplets, it is demonstrated that droplet polymerization is responsible for the formation of large (>1 µm) particles that can lead to coagulum formation. Furthermore, we show that coagulum‐free latexes can be produced using a TEMPO‐mediated ab initio emulsion polymerization by suppressing droplet polymerization.

     

Influence of Ag+ on the Magnetic Response of [2.2.2]Paracyclophane: NMR Properties of a Prototypical Organic Host for Cation Binding Based on DFT Calculations

The complexation of metal cations into a host–guest situation is particularly well exemplified by [2.2.2]paracyclophane and Ag^I, which leads to a strong cation–π interaction with a specific face of the host molecule. Through this study we sought a deeper understanding of the effects the metal center has on the NMR spectroscopic properties of the prototypical organic host, generating theoretical reasons for the observed experimental results with an aim to determine the role of the cation–π interaction in a host–guest scenario. From an analysis of certain components of the induced magnetic field and the ¹³C NMR shielding tensor under its own principal axis system (PAS), the local and overall magnetic behavior can be clearly described. Interestingly, the magnetic response of such a complex exhibits a large axis-dependent behavior, which leads to an overall shielding effect for the coordinating carbon atoms and a deshielding effect for the respective uncoordinated counterparts, evidence that complements previous experimental results. This proposed approach can be useful to gain further insight into the local and overall variation of NMR shifts for host–guest pairs involving both inorganic and organic hosts.     

Modification of Adhesive and Latex Properties for Starch Nanoparticle‐Based Pressure Sensitive Adhesives

Starch nanoparticle (SNP)‐based pressure sensitive adhesives (PSAs) with core‐shell particle morphology (starch nanoparticle core/acrylic polymer shell) are produced via seeded, semi‐batch emulsion polymerization at 15 wt% SNP loading (relative to total polymer weight) and 40 wt% latex solids. Crosslinker and chain transfer agent (CTA) are introduced to the acrylic shell polymer formulation at a range of concentrations according to a 3² factorial design to tailor the latex and adhesive properties of SNP‐based latexes. The crosslinker and CTA show no significant effect on polymerization kinetics, particle size, and viscosity. Latex gel content is predicted using an empirical model, which is a function of crosslinker and CTA concentration. Both the gel content and glass transition temperature strongly affect the adhesive properties (tack, peel strength, and shear strength) of the SNP‐based latex films. 3D response surfaces for the adhesive properties are constructed to facilitate the design of SNP‐based PSAs with desired properties.     

The effect of Co(II)‐mediated catalytic chain transfer on the emulsion polymerization kinetics of methyl methacrylate

The effect the catalytic chain transfer agent, bis[(difluoroboryl) dimethylglyoximato] cobalt(II) (COBF), on the course of the ab initio emulsion polymerization of methyl methacrylate, and the product properties in terms of the molecular weight distribution were investigated. The emulsion polymerization kinetics have been studied with varying surfactant, initiator, and COBF concentrations. The experimentally determined average number of radicals per particle strongly depends on the concentration of COBF and proves to be in good agreement with the results of model calculations. The apparent chain transfer constant, determined up to high conversion, is in excellent agreement with the predicted value based on a mathematical model based on COBF partitioning and the Mayo equation. The results of this work enhance the fundamental understanding of the influence a catalytic chain transfer agent has on the course of the emulsion polymerization and the control of the molecular weight distribution. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5078–5089, 2009     

Calculation and Measurement of Terahertz Active Normal Modes in Crystalline PETN

The terahertz frequency spectrum of pentaerythritol tetranitrate (PETN) is calculated using Discover 1 with the COMPASS 2 force field, CASTEP^[3] and PWscf. 4 The calculations are compared to each other and to terahertz spectra (0.3–3 THz) of crystalline PETN recorded at 4 K. A number of analysis methods are used to characterise the calculated normal modes.     

Properties of a vector soliton laser passively mode-locked by a fiber-based semiconductor saturable absorber operating in transmission

We experimentally demonstrate a passively mode-locked fiber laser employing a fiber-based semiconductor saturable absorber (SSA) operating in transmission. Polarization rotation locked vector solitons are observed in the laser. Due to the intrinsic dynamic feature of the laser, period-doubling of these vector solitons has also been observed. Furthermore, extra spectral sidebands are formed on the optical spectrum, caused by the energy exchange between the two orthogonal polarization components of the vector solitons. By careful reduction of the pump power together with fine adjustment to the cavity birefringence, period-one state can further be obtained. Additionally, the phase noise properties of the vector soliton fiber laser have also been characterized experimentally and analytically.     

DTI at 7 and 3 T: systematic comparison of SNR and its influence on quantitative metrics

Diffusion tensor imaging (DTI) and advanced related methods such as diffusion spectrum and kurtosis imaging are limited by low signal-to-noise ratio (SNR) at conventional field strengths. DTI at 7 T can provide increased SNR; however, B0 and B1 inhomogeneity and shorter T2? still pose formidable challenges. The purpose of this study was to quantify and compare SNR at 7 and 3 T for different parallel imaging reduction factors, R, and TE, and to evaluate SNRs influences on fractional anisotropy (FA) and apparent diffusion coefficient (ADC). We found that R>4 at 7 T and R≥2 at 3 T were needed to reduce geometric distortions due to B0 inhomogeneity. For these R at 7 T, SNR was 70-90 for b=0 s/mm² and 22-28 for b=1000s/mm² in central brain regions. SNR was lower at 3 T (40 for b=0 s/mm² and 15 for b=1000 s/mm²) and in lateral brain regions at 7 T due to B1 inhomogeneity. FA and ADC did not change with MRI field strength, SENSE factor or TE in the tested range. However, the coefficient of variation for FA increased for SNR <15 and for SNR <10 in ADC, consistent with published theoretical studies. Our study demonstrates that 7 T is advantageous for DTI and lays the groundwork for further development. Foremost, future work should further address challenges with B0 and B1 inhomogeneity to take full advantage for the increased SNR at 7 T.