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11.
Absorption and luminescence spectra, depopulation kinetics of the lowest excited singlet and triplet states and acid-base equilibria were investigated for neutral and protonated diazaphenanthrenes: 2,3-, 1,4- and 5,6-DAF. The spectroscopical results are correlated with CNDO/S calculations. Profound influence of topology upon photophysical and chemical (basicity) properties has been stated and discussed. 相似文献
12.
Structural factors affecting the dynamics of the excited state intramolecular proton transfer (ESIPT) are studied for alkyl derivatives of 2,5-bis(2-benzoxazolyl)phenol. Two fluorescence bands with equal decay times are observed in solution, while only one--emitted by the phototautomer--in supersonic jet. All evidence indicates the existence of a potential barrier in the S(1) state. Upon deuteration of the OH group the laser induced fluorescence (LIF) excitation spectra become much sharper as a result of slowing down the proton transfer reaction. Two conformers (rotamers) of each compound in the ground state were detected using hole burning technique. With a help of theoretical calculations three vibrations were identified as the most active ones in reducing the distance between two heavy atoms, N and O, involved in H-bond formation. The widths of (0,0) transitions in LIF excitation spectra decrease with increasing size or number of alkyl substituents at terminal aromatic rings. The corresponding calculated rate constants of ESIPT reaction ( approximately 10(12) s(-1)) decrease approximately three times upon the substituent effect. In contrast, model compound 2,5-bis(2-benzoxazolyl)-4-methoxyphenol (BBMP) with OCH(3) parasubstituent in central ring slows down the ESIPT reaction to such an extent that double, primary and phototautomeric, fluorescences coexist. 相似文献
13.
Fita P Luzina E Dziembowska T Radzewicz C Grabowska A 《The Journal of chemical physics》2006,125(18):184508
The two structurally related Schiff bases, 2-hydroxynaphthylidene-(8-aminoquinoline) (HNAQ) and 2-hydroxynaphthylidene-1(')-naphthylamine (HNAN), were studied by means of steady-state and time resolved optical spectroscopies as well as time-dependent density functional theory (TDDFT) calculations. The first one, HNAQ, is stable as a keto tautomer in the ground state and in the excited state in solutions, therefore it was used as a model of a keto tautomer of HNAN which exists mainly in its enol form in the ground state at room temperature. Excited state intramolecular proton transfer in the HNAN molecule leads to a very weak (quantum yield of the order of 10(-4)) strongly Stokes-shifted fluorescence. The characteristic time of the proton transfer (about 30 fs) was estimated from femtosecond transient absorption data supported by global analysis and deconvolution techniques. Approximately 35% of excited molecules create a photochromic form whose lifetime was beyond the time window of the experiment (2 ns). The remaining ones reach the relaxed S(1) state (of a lifetime of approximately 4 ps), whose emission is present in the decay associated difference spectra. Some evidence for the back proton transfer from the ground state of the keto form with the characteristic time of approximately 13 ps was also found. The energies and orbital characteristics of main electronic transitions in both molecules calculated by TDDFT method are also discussed. 相似文献
14.
Kamila Malecka Iwona Grabowska Jerzy Radecki Anna Stachyra Anna Góra‐Sochacka Agnieszka Sirko Hanna Radecka 《Electroanalysis》2012,24(2):439-446
The working principle of a genosensor is based on the mechanism of ion‐channel mimetic sensors. The analytical signals generated upon hybridization processes were recorded by a redox active marker [Fe(CN)6]3?/4? present in the sample solution using voltammetric techniques. The developed genosensor was suitable for determination of 20‐mer complementary oligonucleotide sequence, and also of the PCR products containing the complementary 20‐mer sequence in various positions, with detection limits in the 10 pM range. The noncomplementary 20‐mer oligonucleotide sequence as well as the PCR product without complementary region generated very weak response. The good discrimination of the position of the complementary part in the PCR products was observed. 相似文献
15.
Ziółek M Kubicki J Maciejewski A Naskrecki R Grabowska A 《The Journal of chemical physics》2006,124(12):124518
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. 相似文献
16.
Ketonization of metameric esters n-hexyl acetate and ethyl n-hexanoate was carried out in the vapor phase over Sn-Ce-Rh-O catalyst at 370°C and at 1 and 3 h-1 load. In both cases the main products were dimethyl ketone, dipentyl ketone and methyl pentyl ketone; however, the compositions and ratios of the products obtained from both esters were different. The transformation pathways of both esters were inferred based on the quantitative differences in the composition of the products. The ratios of the particular compounds obtained during transformation of both esters indicate that the reactions proceeded simultaneously - through -ketoesters with partial thermal decomposition of esters and secondary condensation of the formed aldehydes. Also the way of creation of ketones resulting from secondary condensation was proposed. 相似文献
17.
A scheme combining the preparation of building blocks in solution followed by solid-phase combinatorial chemistry has been developed to side-chain diversify 5-(hydroxymethyl)oxazole scaffold (1) into aryl ethers, thioethers, sulfones, sulfonamides, and carboxamides. Protected heterocyclic scaffolds 2 were linked to the solid phase and N-terminal derivatized using active ester chemistry, providing chemset 4?1-4,1-4?. The free side-chain hydroxyl of 4 was smoothly converted to aryl ethers 6 under Mitsunobu conditions, with a broad range of substituted phenols. Alternatively, quantitative conversion of hydroxyl to bromide followed by displacement with alkyl and aryl thiols gave thioethers 8. Thioethers were optionally oxidized to sulfones 9. Bromide displacement by azide, followed by reduction to amine and acylation with a range of carboxylic acids and sulfonyl chlorides gave carboxamides 11 and sulfonamides 13, respectively. Crude purity at typically >90% was observed for each of the five modifications detailed. A series of 20 compounds, exemplifying each modification, was reprepared, purified, and fully characterized. 相似文献
18.
I. Podolak M. Olech A. Galanty D. Załuski K. Grabowska D. Sobolewska 《Natural product research》2016,30(15):1766-1770
Extracts from leaves and stems of Chenopodium hybridum were characterised for the presence and quantity of flavonoids and phenolic acids by LC-ESI-MS/MS. Five flavonoids and eight phenolic acids were detected for the first time in aerial parts of this plant species, the most abundant compounds being rutin (2.80 μg/g DW), 3-kaempferol rutinoside (2.91 μg/g DW), 4-OH-benzoic (1.86 μg/g DW) and syringic acids (2.31 μg/g DW). Extracts were tested for anti-inflammatory/antiarthritic, antihyaluronidase and cytotoxic activities against human prostate cancer (Du145, PC3) and melanoma cell lines (A375, HTB140 and WM793) of different malignancy. None of the extracts protected bovine serum albumin from heat-induced denaturation. Antihyaluronidase effect at the tested concentration was higher than standard naringenin. Cytotoxic activity was generally low with an exception of the extract from the leaves, which was found most effective against prostate Du145 cell line with 98.28 ± 1.13% of dead cells at 100 μg/mL. 相似文献
19.
Roman Klimkiewicz Hanna Grabowska Ludwik Syper 《Reaction Kinetics and Catalysis Letters》2000,69(1):137-143
The catalytic conversion of esters and mixtures of alcohols and aldehydes in the gas phase over iron oxide has been studied. The method allows for effective synthesis of non-symmetrical ketones. 相似文献
20.
6, 6′-biquinoline (BQ) in aqueous-alcoholic solutions exhibits doubleluminescence and two ESR signals in the triplet state. The structureless fluorescence band observed at room temperature was shown to be the result of the protonation of strongly basic1 (BQ)* (pK* = 13). At low temperature the aggregation of the molecule has been observed. The low temperature absorption, luminescence, luminescence excitation spectra, and triplet ESR spectra of the aggregates have been measured and distinguished from the corresponding spectra of monomeric BQ. 相似文献