Search results for "kytkentä"
showing 10 items of 12 documents
Intermolecular oxidative dehydrogenative 3,3′-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+: total synthesis of shandougenine B
2016
With an excess of a strong acid, 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ) is shown to promote metal-free intermolecular oxidative dehydrogenative (ODH) 3,3'-coupling of 2-aryl-benzo[b]furans and 2-aryl-benzo[b]thiophenes up to 92% yield as demonstrated with 9 substrates. Based on the analysis of oxidation potentials and molecular orbitals combined with EPR, NMR and UV-Vis observations, the studied reaction is initiated by a DDQ-substrate charge transfer complex and presumably proceeds via oxidation of the substrate into an electrophilic radical cation that further reacts with another molecule of a neutral substrate. The coupling reactivity can easily be predicted from the oxidation potent…
Stability of moving viscoelastic panels interacting with surrounding fluid
2012
We study a model describing the out-of-plane vibrations of an axially moving viscoelastic panel submerged in flowing fluid. The panel is assumed to travel at a constant velocity between two fixed supports, and it is modeled as a flat panel made of viscoelastic Kelvin-Voigt material. The fluid flow is modeled with the help of the added mass coefficients. The resulting dynamic equation is a partial differential equation of fifth order in space. Five boundary conditions are set for the studied problem. The behavior of the panel is analyzed with the help of its eigenvalues (eigenfrequencies). These characteristics are studied with respect to the velocity of the panel. In our study, we have incl…
Probabilistic foundations of contextuality
2017
Contextuality is usually defined as absence of a joint distribution for a set of measurements (random variables) with known joint distributions of some of its subsets. However, if these subsets of measurements are not disjoint, contextuality is mathematically impossible even if one generally allows (as one must) for random variables not to be jointly distributed. To avoid contradictions one has to adopt the Contextuality-by-Default approach: measurements made in different contexts are always distinct and stochastically unrelated to each other. Contextuality is reformulated then in terms of the (im)possibility of imposing on all the measurements in a system a joint distribution of a particul…
Conditional convex orders and measurable martingale couplings
2014
Strassen's classical martingale coupling theorem states that two real-valued random variables are ordered in the convex (resp.\ increasing convex) stochastic order if and only if they admit a martingale (resp.\ submartingale) coupling. By analyzing topological properties of spaces of probability measures equipped with a Wasserstein metric and applying a measurable selection theorem, we prove a conditional version of this result for real-valued random variables conditioned on a random element taking values in a general measurable space. We also provide an analogue of the conditional martingale coupling theorem in the language of probability kernels and illustrate how this result can be appli…
Heterogeeniset katalyytit Suzuki-Miyaura -kytkennässä
2016
Suzuki-Miyaura kytkentä on yksi tärkeistä orgaanisen kemian työkaluista, jolla saadaan integroitua hiili-hiilisidoksia molekyyleihin. Tämä palladiumkatalysoitu reaktio on kiinnostanut tutkijoita sen helppouden ja käytännöllisyyden takia jo muutaman vuosikymmenen ajan. Reaktiossa on mahdollista käyttää mm. homogeenisiä katalyyttejä, eli katalyyttejä, jotka sekoittuvat reaktioseokseen eli ovat samassa faasissa (neste/neste) tai heterogeenisiä katalyyttejä, jotka eivät sekoitu reaktioseokseen eli ovat eri faaseissa (neste/kiinteä). Homogeeniset Pd-katalyytit ovat olleet käytössä pitkään mutta niiden käyttöä varjostaa mm. palladiumjäämät reaktioseokseen ja katalyytin erottamisen vaikeus samasta…
Foldameerien isäntä-vieraskemia
2017
Tutkielman kirjallisessa osassa tarkastellaan foldameerejä isäntä-vieraskemian näkökulmasta. Foldameerit voivat sitoa rakenteeseensa erilaisia vierasmolekyylejä, jolloin muodostuu isäntä-vieraskomplekseja. Kirjallisuudesta valittiin tarkasteluun mielenkiintoisimpia anioneja, kationeja ja neutraaleja vierasmolekyylejä sitovia foldameereja ja perehdyttiin niiden vuorovaikutuksiin. Lisäksi tarkasteltiin vierasmolekyylin sitoutumisen aikaansaamia muutoksia foldameerien konformaatiossa. Kokeellisen osan tarkoituksena oli syntetisoida pitkä, 11 aromaattista rengasta sisältävä aryyliamidifoldameeri käyttäen hyväksi pääasiassa peptidikytkentäreaktioita. Koska synteesi osoittautui erittäin haasteell…
Asymmetrical waveguide coupling by a tilted metal nanocone
2017
Kasvava uusiutuvan energian tarve ajaa tiedeyhteisöä etsimään uusia vihreitä energian lähteitä. Osana tätä tavoitetta, WISC-projekti pyrkii yhdistämään infrapunaa keräävän aurinkopaneelin normaaliin ikkunaan. Tässä tutkimuksessa me tutkimme sisääntulevan valon kytkeytymistä kallistuneesta kultananokartiosta laattamaisen aaltojohteen ohjattuihin aaltojohdemoodeihin; tavoitteena on esittää epäsymmetristä aaltojohteeseen kytkeytymistä. Tutkimus suoritettiin simuloimalla Comsolissa käyttäen kolmiulotteista äärellisten elementtien menetelmää. Ulospäin suuntautuva aaltojohteeseen sironneen valon energiavuo mitattiin 2.1 aallonpituuden päässä nanokartiosta. Tulokset viittaavat kahden samanaikaisen…
Identifying Vibrations that Control Non-adiabatic Relaxation of Polaritons in Strongly Coupled Molecule-Cavity Systems
2022
The strong light–matter coupling regime, in which excitations of materials hybridize with excitations of confined light modes into polaritons, holds great promise in various areas of science and technology. A key aspect for all applications of polaritonic chemistry is the relaxation into the lower polaritonic states. Polariton relaxation is speculated to involve two separate processes: vibrationally assisted scattering (VAS) and radiative pumping (RP), but the driving forces underlying these two mechanisms are not fully understood. To provide mechanistic insights, we performed multiscale molecular dynamics simulations of tetracene molecules strongly coupled to the confined light modes of an…
Calculation of magnetic coupling constants with hybrid density functionals
2013
The currently available computational methods for the calculation of magnetic coupling constants with density functional theory have been reviewed. These methods include modern approximations to the exchangecorrelation functional, such as hybrid, range-separated and double-hybrid functionals, as well as approaches to treat the severe spin symmetry problems encountered in density functional calculations of magnetic interactions. In addition to the commonly used unrestricted Kohn–Sham formalism, density functional methods based on multireference wave functions and ensemble densities are also discussed. Performance of these models based on various studies has been summarized. The results indic…