The theoretical ab initio studies of the singlet states of salicylideneaniline (SA) are presented. The enol, cis-keto and trans-keto tautomers were treated by the HF/6-31G* (geometries and force fields of the ground states), and the CIS (excited states), methods. For the dynamic calculations of the rates of proton transfer (PT) in S1 states, the instanton approach was applied. It was found that the SA molecule in S0 and S1 states of both tautomers needs nonplanarity to stabilize. In the ground state the corresponding angle was calculated as 44° vs the experimental value, 49°. Upon twist of the excited system, the conical intersection of (π,π*) and (n,π*) potential surfaces takes place. In enol form the absolute minimum on the S1 potential energy surface belongs to a strongly twisted (n,π*) state. In keto-form this minimum corresponds to a planar (π,π*) state, while the twisted (n,π*) has the energy ≈1055 cm−1 higher. The angles of distortion are equal 93° and 80°, for the enol and keto form, respectively. Both (n,π*) excited tautomers are practically unable to undergo the PT reaction. This, according to the calculations, goes via the planar unstable (π,π*) state. The calculated structures and force-fields lead to the (calculated) proton transfer rate of the order observed experimentally. The calculation of the transfer rate includes multimode nature of the transfer process. The PT cycle of the SA molecule involving the creation of photochromic transient has been proposed.
Transcription factors are key molecules that finely tune gene expression in response to injury. We focused on the role of a transcription factor, Foxn1, whose expression is limited to the skin and thymus epithelium. Our previous studies showed that Foxn1 inactivity in nude mice creates a pro-regenerative environment during skin wound healing. To explore the mechanistic role of Foxn1 in the skin wound healing process, we analyzed post-injured skin tissues from Foxn1::Egfp transgenic and C57BL/6 mice with Western Blotting, qRT-PCR, immunofluorescence and flow cytometric assays. Foxn1 expression in non-injured skin localized to the epidermis and hair follicles. Post-injured skin tissues showed an intense Foxn1-eGFP signal at the wound margin and in leading epithelial tongue, where it co-localized with keratin 16, a marker of activated keratinocytes. This data support the concept that suprabasal keratinocytes, expressing Foxn1, are key cells in the process of re-epithelialization. The occurrence of an epithelial-mesenchymal transition (EMT) was confirmed by high levels of Snail1 and Mmp-9 expression as well as through co-localization of vimentin/E-cadherin-positive cells in dermis tissue at four days post-wounding. Involvement of Foxn1 in the EMT process was verified by co-localization of Foxn1-eGFP cells with Snail1 in histological sections. Flow cytometric analysis showed the increase of double positive E-cadherin/N-cadherin cells within Foxn1-eGFP population of post-wounded skin cells isolates, which corroborated histological and gene expression analyses. Together, our findings indicate that Foxn1 acts as regulator of the skin wound healing process through engagement in re-epithelization and possible involvement in scar formation due to Foxn1 activity during the EMT process.
Two simple, structurally related photochromic Schiff bases, salicylideneaniline (SA) and salicylaldehyde azine (SAA) were studied in femto-and picosecond time domains. In both systems an ultrafast excited state intramolecular proton transfer (ESIPT) reaction was stated with the characteristic time below 50 fs. For SA this result is in contrast to the recent data published by Mitra and Tamai (S.
A photochromic symmetric Schiff base, N,N'-bis(salicylidene)-p-phenylenediamine, is proposed as a probe for the study of solvent dependent enol-keto tautomerism in the ground and excited states. The ground state equilibrium between the enol-keto tautomers is found to depend mainly not on polarity but on the proton donating ability of the solvent. Upon selective excitation of each of these tautomers, the same excited state of a keto tautomer is created: in enol, after the ultrafast excited state intramolecular proton transfer (ESIPT), reaction, and in keto tautomer, directly. Then some part (<30%) of excited molecules are transferred to the photochromic form in its ground state. The evidence of another ultrafast deactivation channel in the excited enol tautomer competing with ESIPT has been found. The solvent does not influence the ESIPT dynamics nor the efficiency of the creation of the photochrome.
The Förster cycle is reconsidered, with emphasis on the thermodynamic approximations and on the necessary experimental precautions. Some examples of acid-base equilibria in excited states are discussed along with new possible applications of the cycle. Der Förster-Zyklus wird neu diskutiert unter Berücksichtigung thormodynamischer Näherungen und möglicher Meßfehler. Einige Beispiele von Säure-Base Gleichgewichten in angeregten Zuständen und neue mögliche Anwendungen des Zyklus werden diskutiert.
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