702 research outputs found
A detailed characterization and design of copolymerization
Many industrial polymerizations are copolymerizations in which two or more comonomers are copolymerized together to obtain a final product with a wide variety of properties originating from the related homopolymers. Crucial is the identification of the correct comonomer types and the reaction conditions so that the suited connectivity of monomer units is ensured in the copolymer chains. In view of this challenge a detailed characterization tool is indispensable. A sole focus on experimental tools is insufficient as they only allow the assessment of copolymer properties through relative properties and/or are limited to average properties [1-4]. The latter implies the lack of validation of intermolecular homogeneities, inhibiting process control on the polymer property level. To solve this issue and thanks to the advance in recent computer technologies, simulation tools have been developed which allow a characterization of copolymerization processes at the molecular level (see Figure 1; [3]). Monomer sequences of individual chains can be visualized allowing an unambiguous product qualification. In this contribution, the potential of these simulation tools is highlighted through several case studies. Focus in on both bulk/solution radical and cationic polymerizations and the interplay of chemistry and diffusional limitations [5-7].
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Designing controlled radical polymerization: A selection of a terminal or penultimate model for the intrinsic reactivities
In the past decades many efforts have been devoted to understand and design controlled radical polymerization (CRP) techniques such as atom transfer radical polymerization (ATRP) and nitroxide mediated polymerization (NMP). A crucial aspect is the use of detailed reaction schemes and the appropriate correction for diffusional limitations. Limited focus has however paid to the impact of penultimate monomer unit (PMU) effects, which can be explained by the complexity of the associated kinetic models with multiple reaction channels and the lack of data on reactivity ratios, in particular for NMP specific reactions. In the present contribution, it is demonstrated that depending on the comonomer pairs and the reaction conditions either a terminal [2] or penultimate model [3] is more suited. For copolymerizations with equimolar conditions for the comonomer amounts the PMU can be very pronounced even if based on the reactivity ratios as such this is not expected (Figure 1).
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Hydrodynamic theory for granular gases
A granular gas subjected to a permanent injection of energy is described by
means of hydrodynamic equations derived from a moment expansion method. The
method uses as reference function not a Maxwellian distribution but
a distribution , such that adds a fourth cumulant
to the velocity distribution. The formalism is applied to a stationary
conductive case showing that the theory fits extraordinarily well the results
coming from our molecular dynamic simulations once we determine as a
function of the inelasticity of the particle-particle collisions. The shape of
is independent of the size of the system.Comment: 10 pages, 9 figures, more about our research in
http://www.cec.uchile.cl/cinetica
A novel interpretation of measured and simulated PLP data
Figure 1 - Simulated ν dependency of the observed kp in vinyl acetate PLP at 323 K. Case 1 (♦): chain length independent head-to-tail prop., Case 2 (■): chain length dependent head-to-tail prop., Case 3 (●): chain length dependent head-to-tail, head-to-head, tail-to-tail, and tail-to-head prop., and Case 4 (▲): Case 3 with backbiting by head and tail radicals, and mid-chain prop.
Pulsed laser polymerization (PLP) is an interesting technique to study individual reactions.1-4 In PLP, photoinitiator radical fragments are generated at laser pulses with a frequency ν (or dark time Δt = ν-1). Depending on the PLP conditions and the monomer type, the molar mass distribution (MMD) can possess specific characteristics, allowing the determination of intrinsic rate coefficients. Most known is that under well-chosen conditions a multimodal MMD with inflection points Lj (j = 1, 2, …) is obtained, allowing the determination of the propagation rate coefficient kp ([M]0: initial monomer concentration):
(1)
In this contribution, kinetic Monte Carlo (kMC) modeling is applied to allow a further understanding and exploitation of PLP. For PLP of acrylates, regression analysis to low frequency inflection point data at various solvent volume fractions is proposed as an additional new method to estimate the backbiting rate coefficient kbb.5 Moreover, it is demonstrated that photodissociation, chain initiation and termination reactivities can be extracted from the complete PLP MMD.6 For the first time, the ratio of MMD peak heights has been used for the fast and reliable estimation of the photodissociation quantum yield,Φ.7
For PLP of vinyl acetate a unique combination of ab initio calculated rate coefficients and kMC simulations is considered to explain the experimental8 ν dependency of the observed kp (cf. Case 4 in Figure 1; Eq. (1) with kpobs). Via a stepwise extension of the kMC model (cf. 4 cases in Figure 1), the ν dependency is attributed to backbiting of tail radicals formed via head-to-head propagation.9 In contrast to acrylates, backbiting of head radicals is shown to be kinetically insignificant in VAc PLP, further highlighting the chemical difference between both vinyl monomer types.
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Flow of excitation energy in the cryptophyte light-harvesting antenna phycocyanin 645.
We report a detailed description of the energy migration dynamics in the phycocyanin 645 (PC645) antenna complex from the photosynthetic alga Chroomonas CCMP270. Many of the cryptophyceae are known to populate greater depths than most other algal families, having developed a 99.5% efficient light-harvesting system. In this study, we used femtosecond time-resolved spectroscopy and global analysis to characterize the excited-state dynamics of PC645. Several different pump colors were selected to excite different fractions of the four phycobiliprotein pairs present in the complex. Measurements were also performed at cryogenic temperature to enhance spectral resolution and selectively promote downhill energy transfers. Upon excitation of the highest-energy bilins (dihydrobiliverdins), energy is transferred from the core of the complex to the periphery within 0.82 ps. Four bilins (mesobiliverdin (MBV) A/B and phycocyanobilins (PCB) 158C/D), which are responsible for the central band of the absorption spectrum, show concerted spectral dynamics. These chromophores show a biphasic decay with lifetimes of 0.6 ps (MBV) and 5-7 ps (PCB 158) to the lowest bilin pair (PCB 82C/D) absorbing around 650-657 nm. Within this lifetime of several picoseconds, the excitations reach the PCB 82 bilins on the two poles at the smaller sides of PC645. A slow 44-46 ps energy transfer step to the lowest-energy PCB 82 bilin concludes the dynamics. © 2011 Biophysical Society
Search for composite and exotic fermions at LEP 2
A search for unstable heavy fermions with the DELPHI detector at LEP is
reported. Sequential and non-canonical leptons, as well as excited leptons and
quarks, are considered. The data analysed correspond to an integrated
luminosity of about 48 pb^{-1} at an e^+e^- centre-of-mass energy of 183 GeV
and about 20 pb^{-1} equally shared between the centre-of-mass energies of 172
GeV and 161 GeV. The search for pair-produced new leptons establishes 95%
confidence level mass limits in the region between 70 GeV/c^2 and 90 GeV/c^2,
depending on the channel. The search for singly produced excited leptons and
quarks establishes upper limits on the ratio of the coupling of the excited
fermio
Search for charginos in e+e- interactions at sqrt(s) = 189 GeV
An update of the searches for charginos and gravitinos is presented, based on
a data sample corresponding to the 158 pb^{-1} recorded by the DELPHI detector
in 1998, at a centre-of-mass energy of 189 GeV. No evidence for a signal was
found. The lower mass limits are 4-5 GeV/c^2 higher than those obtained at a
centre-of-mass energy of 183 GeV. The (\mu,M_2) MSSM domain excluded by
combining the chargino searches with neutralino searches at the Z resonance
implies a limit on the mass of the lightest neutralino which, for a heavy
sneutrino, is constrained to be above 31.0 GeV/c^2 for tan(beta) \geq 1.Comment: 22 pages, 8 figure
Measurements of long-range near-side angular correlations in TeV proton-lead collisions in the forward region
Two-particle angular correlations are studied in proton-lead collisions at a
nucleon-nucleon centre-of-mass energy of TeV, collected
with the LHCb detector at the LHC. The analysis is based on data recorded in
two beam configurations, in which either the direction of the proton or that of
the lead ion is analysed. The correlations are measured in the laboratory
system as a function of relative pseudorapidity, , and relative
azimuthal angle, , for events in different classes of event
activity and for different bins of particle transverse momentum. In
high-activity events a long-range correlation on the near side, , is observed in the pseudorapidity range . This
measurement of long-range correlations on the near side in proton-lead
collisions extends previous observations into the forward region up to
. The correlation increases with growing event activity and is found
to be more pronounced in the direction of the lead beam. However, the
correlation in the direction of the lead and proton beams are found to be
compatible when comparing events with similar absolute activity in the
direction analysed.Comment: All figures and tables, along with any supplementary material and
additional information, are available at
https://lhcbproject.web.cern.ch/lhcbproject/Publications/LHCbProjectPublic/LHCb-PAPER-2015-040.htm
Study of the production of and hadrons in collisions and first measurement of the branching fraction
The product of the () differential production
cross-section and the branching fraction of the decay () is
measured as a function of the beauty hadron transverse momentum, ,
and rapidity, . The kinematic region of the measurements is and . The measurements use a data sample
corresponding to an integrated luminosity of collected by the
LHCb detector in collisions at centre-of-mass energies in 2011 and in 2012. Based on previous LHCb
results of the fragmentation fraction ratio, , the
branching fraction of the decay is
measured to be \begin{equation*} \mathcal{B}(\Lambda_b^0\rightarrow J/\psi
pK^-)= (3.17\pm0.04\pm0.07\pm0.34^{+0.45}_{-0.28})\times10^{-4},
\end{equation*} where the first uncertainty is statistical, the second is
systematic, the third is due to the uncertainty on the branching fraction of
the decay , and the
fourth is due to the knowledge of . The sum of the
asymmetries in the production and decay between and
is also measured as a function of and .
The previously published branching fraction of , relative to that of , is updated.
The branching fractions of are determined.Comment: 29 pages, 19figures. All figures and tables, along with any
supplementary material and additional information, are available at
https://lhcbproject.web.cern.ch/lhcbproject/Publications/LHCbProjectPublic/LHCb-PAPER-2015-032.htm
Evidence for the strangeness-changing weak decay
Using a collision data sample corresponding to an integrated luminosity
of 3.0~fb, collected by the LHCb detector, we present the first search
for the strangeness-changing weak decay . No
hadron decay of this type has been seen before. A signal for this decay,
corresponding to a significance of 3.2 standard deviations, is reported. The
relative rate is measured to be
, where and
are the and fragmentation
fractions, and is the branching
fraction. Assuming is bounded between 0.1 and
0.3, the branching fraction would lie
in the range from to .Comment: 7 pages, 2 figures, All figures and tables, along with any
supplementary material and additional information, are available at
https://lhcbproject.web.cern.ch/lhcbproject/Publications/LHCbProjectPublic/LHCb-PAPER-2015-047.htm
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