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41.
42.
Kamil Walczak 《Central European Journal of Physics》2006,4(2):241-253
In this work we study the effect of decoherence on elastic and polaronic transport via discrete quantum states. Calculations
are performed with the help of a nonperturbative computational scheme, based on Green’s function theory within the framework
of polaron transformation (GFT-PT), where the many-body electron-phonon interaction problem is mapped exactly into a single-electron
multi-channel scattering problem. In particular, the influence of dephasing and relaxation processes on the shape of the electrical
current and shot noise curves is discussed in detail under linear and nonlinear transport conditions. 相似文献
43.
44.
Tomasz GoslinskiTomasz Osmalek Krystyna KonopkaMarcin Wierzchowski Piotr Fita Jadwiga Mielcarek 《Polyhedron》2011,30(9):1538-1546
Two novel zinc(II) phthalocyanines bearing non-peripheral ester-alkyloxy substituents (Pc-4 and Pc-5) were synthesized, by a two-step procedure starting from 2,3-dicyanohydroquinone. Both sensitizers show promising photophysical properties, including solvatochromic study, qualitative evaluation of emission, aggregation behavior and singlet oxygen generation. It was proven that the photodynamic activity of the compounds studied depends on the molecular oxygen level. Comparison of the quantum yields of singlet oxygen generation as well as the oxidation rate constants using 1,3-diphenylisobenzofurane before and after deaeration proved the photodynamic effect of Pc-4 and Pc-5 to be governed by the photosensitization mechanism II. Changes in the quantities of the compounds exposed to irradiation were also estimated. Upon their exposure to light the changes in intensity of the Q band were monitored. The photodecomposition of Pc-4 and Pc-5 in DMSO or DMF solutions was found to proceed according to the first order kinetic reaction in two stages.The photosensitizing effect of Pc-4 in HSC-3 cells was significantly lower than that of ZnPc. Pc-4 was ineffective at 0.1 μM, while a low, approx. 15% photocytotoxicity was observed at 5 μM, at a distance of 5 and 10 cm. The efficacy of Pc-4 in photokilling of cultured cells is affected by hydrophobicity and the aggregation status of the photosensitizer. 相似文献
45.
Liu G Liang Y Bar-Shir A Chan KW Galpoththawela CS Bernard SM Tse T Yadav NN Walczak P McMahon MT Bulte JW van Zijl PC Gilad AA 《Journal of the American Chemical Society》2011,133(41):16326-16329
Chemical exchange saturation transfer (CEST) is a new approach for generating magnetic resonance imaging (MRI) contrast that allows monitoring of protein properties in vivo. In this method, a radiofrequency pulse is used to saturate the magnetization of specific protons on a target molecule, which is then transferred to water protons via chemical exchange and detected using MRI. One advantage of CEST imaging is that the magnetizations of different protons can be specifically saturated at different resonance frequencies. This enables the detection of multiple targets simultaneously in living tissue. We present here a CEST MRI approach for detecting the activity of cytosine deaminase (CDase), an enzyme that catalyzes the deamination of cytosine to uracil. Our findings suggest that metabolism of two substrates of the enzyme, cytosine and 5-fluorocytosine (5FC), can be detected using saturation pulses targeted specifically to protons at +2 ppm and +2.4 ppm (with respect to water), respectively. Indeed, after deamination by recombinant CDase, the CEST contrast disappears. In addition, expression of the enzyme in three different cell lines exhibiting different expression levels of CDase shows good agreement with the CDase activity measured with CEST MRI. Consequently, CDase activity was imaged with high-resolution CEST MRI. These data demonstrate the ability to detect enzyme activity based on proton exchange. Consequently, CEST MRI has the potential to follow the kinetics of multiple enzymes in real time in living tissue. 相似文献
46.
Maślanka A Krzek J Stolarczyk M Walczak M Głogowska A 《Journal of AOAC International》2011,94(6):1791-1799
Stability of clonazepam, diazepam, haloperidol, and doxepin was determined in acidic solutions. In addition, determination of the kinetic and thermodynamic properties of this stability was carried out. Reaction rate constants (k), half-life times (t(0.1) and t(0.5)), and activation energy (Ea) were estimated for the drugs, which differed in polarity expressed with log P values. It was observed that estimated Ea values increased from 42.13 to 125.03 kJ/mol with an increase of lipophilicity (log P) beginning from the most hydrophilic drug (clonazepam, 2.70 log P) to the most lipophilic drug (doxepin, 4.10 log P). All degradation products were studied using an HPLC/electrospray ionization-MS technique in the positive ionization mode. 相似文献
47.
Woźnica M Butkiewicz A Grzywacz A Kowalska P Masnyk M Michalak K Luboradzki R Furche F Kruse H Grimme S Frelek J 《The Journal of organic chemistry》2011,76(9):3306-3319
In the present work, the validity of the helicity rule relating the absolute configuration of the bridgehead carbon atom in bicyclic β-lactams to the sign of the 220 nm band observed in their electronic circular dichroism (ECD) spectra is examined for ring-expanded cephalosporin analogues. To this end, a series of model compounds with a seven-membered ring condensed with the β-lactam unit was synthesized. A key step of their synthesis was either the ring-closing metathesis (RCM) or the free radical cyclization leading to the seven-membered ring with an S, O, or C atom at the 6 position in the bicyclic skeleton. To investigate the scope and limitations of the simple, empirically established helicity rule, a combination of ECD spectroscopy, variable-temperature ECD measurements, X-ray analysis, and time-dependent density functional theory (TD-DFT) calculations was used. A comparison of the experimental ECD spectra with the spectra simulated by TD-DFT calculations gives a reasonable interpretation of the Cotton effects observed in the 240-215 nm spectral range. The results suggest that the helicity rule does not apply to the investigated compounds because of the planarity of their amide chromophore. Thus, these compounds do not constitute an exception to the rule that was established for bi- and polycyclic β-lactams with the nonplanar amide chromophore only. 相似文献
48.
Detection of apoptosis is one of the main criteria of preimplantation embryo growth potential assessment. Recent developments in lab-on-a-chip techniques has led to apoptosis detection and monitoring on a single cell or embryo level. However, single embryo apoptosis detection without a change in embryo developmental competence and post-examination "recovery" still remains a challenge. In this paper we present a lab-on-a-chip, co-working with miniaturized optical instrumentation, which allows supravital examination of single embryos for the presence of apoptotic blastomers with full after lab-on-a-chip study "recovery" and maintenance of their further developmental capacity. 相似文献
49.
The influence of charging effects on the transport characteristics of a molecular wire bridging two metallic electrodes in the limit of weak contacts is studied by the generalized Breit–Wigner formula. Molecule is modeled as a quantum dot with discrete energy levels, while the coupling to the electrodes is treated within a broad-band theory. Owing to this model we find self-consistent occupation of particular energy levels and orbital energies of the wire in the presence of transport. The nonlinear conductance and current–voltage characteristics are investigated as a function of bias voltage in the case of symmetric and asymmetric coupling to the electrodes. It is shown that the shape of those curves are determined by the combined effect of the electronic structure of the molecule and by electron–electron repulsion. 相似文献
50.
Jadwiga Mielcarek Magdalena Kula Róa Zych Pawe Grobelny 《Reaction Kinetics and Catalysis Letters》2005,86(1):119-126
Summary The effect of solvent on the photodegradation kinetics of fluvastatin was evaluated. The degradation rate of fluvastatin was estimated on the basis of the quantum yields and kinetic parameters determination. The photodegradation appeared to follow first-order kinetics. In order to establish the light intensity absorbed by a system, Reinecke’s salt was used as a chemical actinometer. 相似文献