Investigations into Ring-Opening Polymerization of Functionalized ϵ-Caprolactones

Polymers are defined as large molecules constructed from small, repeating units (monomers) which make up everyday items, such as: plastic bags and bottles, waterproof coatings, pipes, etc. H-bonding urea (U) or thiourea (TU) catalysts paired with base cocatalysts used for organocatalytic ring-opening polymerization (ROP) of cyclic esters have been shown to exhibit fast rates of polymerization and result in polymers with controlled molecular weights (Mn) and low polydispersity indexes (PDI). Additionally, organocatalytic ring-opening polymerization (ROP) techniques have been shown to be tolerant of the incorporation of functional groups into the monomer feed, which is vital for the catalytic synthesis of biologically active polymers. H-bonding catalysts have seen considerable gains in the field of ROP recently, delivering fast reaction rates to rival that seen in metal-based catalysts but with enhanced control of Mn, PDI and functional group incorporation. Variation of the substituent position on the monomer allows for optimization of the material properties, such as: solubility, polarity, thermal, and mechanical. This research investigated the kinetics of H-bonding organic catalysts for the ROP of the functionalized monomers of interest (5-MeCL, 6-MeCL, and TOSUO). Until this point, these new monomers have only been polymerized to approximately 7% conversion after 8 days with a commonly used guanidine base organocatalyst for ROP. Using the dual H-bonding catalysts, whose electronics can be modified, along with different commercially available bases, provides a more tunable approach for the ROP of functionalized lactones

Measurement of the pn→ppπ0π−pn \to pp\pi^0\pi^- Reaction in Search for the Recently Observed Resonance Structure in dπ0π0d\pi^0\pi^0 and dπ+π−d\pi^+\pi^- systems

Exclusive measurements of the quasi-free $pn \to pp\pi^0\pi^-$ reaction have been performed by means of $pd$ collisions at $T_p$ = 1.2 GeV using the WASA detector setup at COSY. Total and differential cross sections have been obtained covering the energy region $\sqrt s$ = (2.35 - 2.46) GeV, which includes the region of the ABC effect and its associated resonance structure. No ABC effect, {\it i.e.} low-mass enhancement is found in the $\pi^0\pi^-$-invariant mass spectrum -- in agreement with the constraint from Bose statistics that the isovector pion pair can not be in relative s-wave. At the upper end of the covered energy region $t$-channel processes for Roper, $\Delta(1600)$ and $\Delta\Delta$ excitations provide a reasonable description of the data, but at low energies the measured cross sections are much larger than predicted by such processes. Adding a resonance amplitude for the resonance at $m$=~2.37 GeV with $\Gamma$ =~70 MeV and $I(J^P)=~0(3^+)$ observed recently in $pn \to d\pi^0\pi^0$ and $pn \to d\pi^+\pi^-$ reactions leads to an agreement with the data also at low energies

Cross section ratio and angular distributions of the reaction p + d -> 3He + eta at 48.8 MeV and 59.8 MeV excess energy

We present new data for angular distributions and on the cross section ratio of the p + d -> 3He + eta reaction at excess energies of Q = 48.8 MeV and Q = 59.8 MeV. The data have been obtained at the WASA-at-COSY experiment (Forschungszentrum J\"ulich) using a proton beam and a deuterium pellet target. While the shape of obtained angular distributions show only a slow variation with the energy, the new results indicate a distinct and unexpected total cross section fluctuation between Q = 20 MeV and Q = 60 MeV, which might indicate the variation of the production mechanism within this energy interval.Comment: 9 pages, 9 figure

Evidence for a New Resonance from Polarized Neutron-Proton Scattering

Exclusive and kinematically complete high-statistics measurements of quasifree polarized $\vec{n}p$ scattering have been performed in the energy region of the narrow resonance structure $d^*$ with $I(J^P) = 0(3^+)$, $M \approx$ 2380 MeV/$c^2$ and $\Gamma \approx$ 70 MeV observed recently in the double-pionic fusion channels $pn \to d\pi^0\pi^0$ and $pn \to d\pi^+\pi^-$. The experiment was carried out with the WASA detector setup at COSY having a polarized deuteron beam impinged on the hydrogen pellet target and utilizing the quasifree process $\vec{d}p \to np + p_{spectator}$. That way the $np$ analyzing power $A_y$ was measured over a large angular range. The obtained $A_y$ angular distributions deviate systematically from the current SAID SP07 NN partial-wave solution. Incorporating the new $A_y$ data into the SAID analysis produces a pole in the $^3D_3 - ^3G_3$ waves as expected from the $d^*$ resonance hypothesis

Specific involvement of atypical PKCζ/PKMζ in spinal persistent nociceptive processing following peripheral inflammation in rat.

BACKGROUND: Central sensitization requires the activation of various intracellular signalling pathways within spinal dorsal horn neurons, leading to a lowering of activation threshold and enhanced responsiveness of these cells. Such plasticity contributes to the manifestation of chronic pain states and displays a number of features of long-term potentiation (LTP), a ubiquitous neuronal mechanism of increased synaptic strength. Here we describe the role of a novel pathway involving atypical PKCζ/PKMζ in persistent spinal nociceptive processing, previously implicated in the maintenance of late-phase LTP. RESULTS: Using both behavioral tests and in vivo electrophysiology in rats, we show that inhibition of this pathway, via spinal delivery of a myristoylated protein kinase C-ζ pseudo-substrate inhibitor, reduces both pain-related behaviors and the activity of deep dorsal horn wide dynamic range neurons (WDRs) following formalin administration. In addition, Complete Freund's Adjuvant (CFA)-induced mechanical and thermal hypersensitivity was also reduced by inhibition of PKCζ/PKMζ activity. Importantly, this inhibition did not affect acute pain or locomotor behavior in normal rats and interestingly, did not inhibited mechanical allodynia and hyperalgesia in neuropathic rats. Pain-related behaviors in both inflammatory models coincided with increased phosphorylation of PKCζ/PKMζ in dorsal horn neurons, specifically PKMζ phosphorylation in formalin rats. Finally, inhibition of PKCζ/PKMζ activity decreased the expression of Fos in response to formalin and CFA in both superficial and deep laminae of the dorsal horn. CONCLUSIONS: These results suggest that PKCζ, especially PKMζ isoform, is a significant factor involved in spinal persistent nociceptive processing, specifically, the manifestation of chronic pain states following peripheral inflammation

ABC Effect in Basic Double-Pionic Fusion --- Observation of a new resonance?

We report on a high-statistics measurement of the basic double pionic fusion reaction $pn \to d\pi^0\pi^0$ over the energy region of the so-called ABC effect, a pronounced low-mass enhancement in the $\pi\pi$-invariant mass spectrum. The measurements were performed with the WASA detector setup at COSY. The data reveal the ABC effect to be associated with a Lorentzian shaped energy dependence in the integral cross section. The observables are consistent with a resonance with $I(J^P) =0(3^+)$ in both $pn$ and $\Delta\Delta$ systems. Necessary further tests of the resonance interpretation are discussed

Removing krypton from xenon by cryogenic distillation to the ppq level

The XENON1T experiment aims for the direct detection of dark matter in a cryostat filled with 3.3 tons of liquid xenon. In order to achieve the desired sensitivity, the background induced by radioactive decays inside the detector has to be sufficiently low. One major contributor is the $\beta$-emitter $^{85}$Kr which is an intrinsic contamination of the xenon. For the XENON1T experiment a concentration of natural krypton in xenon $\rm{^{nat}}$Kr/Xe < 200 ppq (parts per quadrillion, 1 ppq = 10$^{-15}$ mol/mol) is required. In this work, the design of a novel cryogenic distillation column using the common McCabe-Thiele approach is described. The system demonstrated a krypton reduction factor of 6.4$\cdot$10$^5$ with thermodynamic stability at process speeds above 3 kg/h. The resulting concentration of $\rm{^{nat}}$Kr/Xe < 26 ppq is the lowest ever achieved, almost one order of magnitude below the requirements for XENON1T and even sufficient for future dark matter experiments using liquid xenon, such as XENONnT and DARWIN

Neutron-Proton Scattering in the Context of the d∗d^*(2380) Resonance

New data on quasifree polarized neutron-proton scattering, in the region of the recently observed $d^*$ resonance structure, have been obtained by exclusive and kinematically complete high-statistics measurements with WASA at COSY. This paper details the determination of the beam polarization, checks of the quasifree character of the scattering process, on all obtained $A_y$ angular distributions and on the new partial-wave analysis, which includes the new data producing a resonance pole in the $^3D_3$-$^3G_3$ coupled partial waves at ($2380\pm10 - i40\pm5$) MeV -- in accordance with the $d^*$ dibaryon resonance hypothesis. The effect of the new partial-wave solution on the description of total and differential cross section data as well as specific combinations of spin-correlation and spin-transfer observables available from COSY-ANKE measurements at $T_d$ = 2.27 GeV is discussed

ABC Effect and Resonance Structure in the Double-Pionic Fusion to 3^3He

Exclusive and kinematically complete measurements of the double pionic fusion to $^3$He have been performed in the energy region of the so-called ABC effect, which denotes a pronounced low-mass enhancement in the $\pi\pi$-invariant mass spectrum. The experiments were carried out with the WASA detector setup at COSY. Similar to the observations in the basic $pn \to d \pi^0\pi^0$ reaction and in the $dd \to ^4$He$\pi^0\pi^0$ reaction, the data reveal a correlation between the ABC effect and a resonance-like energy dependence in the total cross section. Differential cross sections are well described by the hypothesis of $d^*$ resonance formation during the reaction process in addition to the conventional $t$-channel $\Delta\Delta$ mechanism. The deduced $d^*$ resonance width can be understood from collision broadening due to Fermi motion of the nucleons in initial and final nuclei