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RISS 인기검색어
- 검색키워드
- 저자 : Łukasiewicz, Łukasz G. (검색결과 3 건)
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Łukasiewicz, Łukasz G.,Ryu, Hye Gun,Mikhaylov, Alexander,Azarias, Cloé,Banasiewicz, Marzena,Kozankiewicz, Bolesław,Ahn, Kyo Han,Jacquemin, Denis,Rebane, Aleksander,Gryko, Daniel T. Wiley (John WileySons) 2017 Chemistry, an Asian journal Vol.12 No.14
<P>Five centrosymmetric and one dipolar pyrrolo[3,2-b]pyrroles, possessing either two or one strongly electron-withdrawing nitro group have been synthesized in a straightforward manner from simple building blocks. For the symmetric compounds, the nitroaryl groups induced spontaneous breaking of inversion symmetry in the excited state, thereby leading to large solvatofluorochromism. To study the origin of this effect, the series employed peripheral structural motifs that control the degree of conjugation via altering of dihedral angle between the 4-nitrophenyl moiety and the electron-rich core. We observed that for compounds with a larger dihedral angle, the fluorescence quantum yield decreased quickly when exposed to even moderately polar solvents. Reducing the dihedral angle (i.e., placing the nitrobenzene moiety in the same plane as the rest of the molecule) moderated the dependence on solvent polarity so that the dye exhibited significant emission, even in THF. To investigate at what stage the symmetry breaking occurs, we measured two-photon absorption (2PA) spectra and 2PA cross-sections (sigma(2PA)) for all six compounds. The 2PA transition profile of the dipolar pyrrolo[3,2-b]pyrrole, followed the corresponding one-photon absorption (1PA) spectrum, which provided an estimate of the change of the permanent electric dipole upon transition, approximate to 18D. The nominally symmetric compounds displayed an allowed 2PA transition in the wavelength range of 700-900nm. The expansion via a triple bond resulted in the largest peak value, sigma(2PA)=770GM, whereas altering the dihedral angle had no effect other than reducing the peak value two- or even three-fold. In the S0S1 transition region, the symmetric structures also showed a partial overlap between 2PA and 1PA transitions in the long-wavelength wing of the band, from which a tentative, relatively small dipole moment change, 2-7D, was deduced, thus suggesting that some small symmetry breaking may be possible in the ground state, even before major symmetry breaking occurs in the excited state.</P>
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Use of custom glenoid components for reverse total shoulder arthroplasty
Punyawat Apiwatanakul,Prashant Meshram,Andrew B. Harris,Joel Bervell,Piotr Łukasiewicz,Ridge Maxson,Matthew J Best,Edward G. McFarland 대한견주관절학회 2023 대한견주관절의학회지 Vol.26 No.4
Background: Our purpose was to evaluate a custom reverse total shoulder arthroplasty glenoid baseplate for severe glenoid deficiency, emphasizing the challenges with this approach, including short-term clinical and radiographic outcomes and complications. Methods: This was a single-institution, retrospective series of 29 patients between January 2017 and December 2022 for whom a custom glenoid component was created for extensive glenoid bone loss. Patients were evaluated preoperatively and at intervals for up to 5 years. All received preoperative physical examinations, plain radiographs, and computed tomography (CT). Intra- and postoperative complications are reported. Results: Of 29 patients, delays resulted in only undergoing surgery, and in three of those, the implant did not match the glenoid. For those three, the time from CT scan to implantation averaged 7.6 months (range, 6.1–10.7 months), compared with 5.5 months (range, 2–8.6 months) for those whose implants fit. In patients with at least 2-year follow-up (n=9), no failures occurred. Significant improvements were observed in all patient-reported outcome measures in those nine patients (American Shoulder and Elbow Score, P<0.01; Simple Shoulder Test, P=0.02; Single Assessment Numeric Evaluation, P<0.01; Western Ontario Osteoarthritis of the Shoulder Index, P<0.01). Range of motion improved for forward flexion and abduction (P=0.03 for both) and internal rotation up the back (P=0.02). Pain and satisfaction also improved (P<0.01 for both). Conclusions: Prolonged time (>6 months) from CT scan to device implantation resulted in bone loss that rendered the implants unusable. Satisfactory short-term radiographic and clinical follow-up can be achieved with a well-fitting device. Level of evidence: III.
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Bidirectional Solvatofluorochromism of a Pyrrolo[3,2-<i>b</i>]pyrrole-Diketopyrrolopyrrole Hybrid
Ryu, Hye Gun,Mayther, Maximillian F.,Tamayo, Jesse,Azarias, Cloé,Espinoza, Eli M.,Banasiewicz, Marzena,Łukasiewicz, Łukasz G.,Poronik, Yevgen M.,Jeż,ewski, Artur,Clark, John,Derr, James B. American Chemical Society 2018 The Journal of Physical Chemistry Part C Vol.122 No.25
<P>Hybridization of electron donors and acceptors provides routes to long-wavelength absorbing and fluorescing dyes. Varying the coupling of low-lying charge-transfer (CT) states with the ground and different locally excited states profoundly affects the photophysics of such donor-acceptor conjugates. Herein, we hybridize an electron-deficient diketopyrrolopyrrole (DPP) moiety with an electron-rich pyrrolopyrrole (PP) that is symmetrically N-arylated with 4-nitrophenyl substituents. The lowest Franck-Condon state is located on the DPP ring structure and dominates the photophysics of the hybrid. Similar to the DPP moiety, the hybrid exhibits optical absorption that is invariant to the solvent media. The PP donor considerably modulates its fluorescence by undergoing electron transfer to the locally excited DPP to form a CT state. For nonpolar media, an increase in solvent polarity causes a bathochromic shift of the fluorescence reaching the longest wavelengths for chloroform and DCM. A further increase in the medium polarity moves the fluorescence maximum hypsochromically back to where it is for alkane solvents. This bidirectional solvatofluorochromism accompanies a polarity-induced increase in the nonradiative decay rates leading to a decrease in the emission quantum yield. The solvent dependence of the energy level of the CT state is responsible for the observed polarity-induced fluorescence behavior of the hybrid. This emission behavior, along with the solvent invariance of the absorption, results in multimodal sensitivity to the solvation environment.</P> [FIG OMISSION]</BR>
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