This work examines the influence of applied external voltage in bulk electrolysis on the excited-state properties of 8'-apo-β-carotenal in acetonitrile by steady-state and ultrafast time-resolved absorption spectroscopy. The data collected under bulk electrolysis were compared with those taken without applied voltage. The steady-state measurements showed that although intensity of the S0 -S2 absorption band varies with the applied voltage, the spectral position remain nearly constant. Comparison of transient absorption spectra shows that the magnitude of the ICT-like band decreases during the experiment under applied voltage condition, and is associated with a prolongation of the S1 /ICT-like lifetime from 8 ps to 13 ps. Furthermore, switching off the applied voltage resulted in returning to no-voltage data within about 30 min. Our results show that the amplitude of the signal associated with the ICT state can be tuned by applying an external voltage.

• Klíčová slova
• 8’-apo-β-carotenal, carotenoid, cyclic voltammetry, spectroelectrochemistry, transient absorption,
• Publikační typ
• časopisecké články MeSH

Non-covalent functionalization of single wall carbon nanotubes (SWCNTs) has been conducted using several binding agents with surface π-interaction forces in recent studies. Herein, we present the first example of non-covalent functionalization of sidewalls of SWCNTs using thienothiophene (TT) derivatives without requiring any binding agents. Synthesized TT derivatives, TT-CN-TPA, TT-CN-TPA2 and TT-COOH-TPA, were attached directly to SWCNTs through non-covalent interactions to obtain new TT-based SWCNT hybrids, HYBRID 1-3. Taking advantage of the presence of sulfur atoms in the structure of TT, HYBRID 1, as a representative, was treated with Au nanoparticles for the adsorption of Au by sulfur atoms, which generated clear TEM images of the particles. The images indicated the attachment of TTs to the surface of SWCNTs. Thus, the presence of sulfur atoms in TT units made the binding of TTs to SWCNTs observable via TEM analysis through adsorption of Au nanoparticles by the sulfur atoms. Surface interactions between TTs and SWCNTs of the new hybrids were also clarified by classical molecular dynamic simulations, a quantum mechanical study, and SEM, TEM, AFM and contact angle (CA) analyses. The minimum distance between a TT and a SWCNT reached up to 3.5 Å, identified with strong peaks on a radial distribution function (RDF), while maximum interaction energies were raised to -316.89 kcal mol-1, which were determined using density functional theory (DFT).

• Publikační typ
• časopisecké články MeSH

We used ultrafast transient absorption spectroscopy to study excited-state dynamics of the keto-carotenoid fucoxanthin (Fx) and its two derivatives: 19'-butanoyloxyfucoxanthin (bFx) and 19'-hexanoyloxyfucoxanthin (hFx). These derivatives occur in some light-harvesting systems of photosynthetic microorganisms, and their presence is typically related to stress conditions. Even though the hexanoyl (butanoyl) moiety is not a part of the conjugated system of hFx (bFx), their absorption spectra in polar solvents exhibit more pronounced vibrational bands of the S2 state than for Fx. The effect of the nonconjugated acyloxy moiety is further observed in transient absorption spectra, which for Fx exhibit characteristic features of an intramolecular charge transfer (ICT) state in all polar solvents. For bFx and hFx, however, much weaker ICT features are detected in methanol, and the spectral markers of the ICT state disappear completely in polar, but aprotic acetonitrile. The presence of the acyloxy moiety also alters the lifetimes of the S1/ICT state. For Fx, the lifetimes are 60, 30, and 20 ps in n-hexane, acetonitrile, and methanol, whereas for bFx and hFx, these lifetimes yield 60, 60, and 40 ps, respectively. Testing the S1/ICT state lifetimes of hFx in other solvents revealed that some ICT features can be induced only in polar, protic solvents (methanol, ethanol, and ethylene glycol). Thus, bFx and hFx represent a rather rare example of a system in which a nonconjugated functional group significantly alters excited-state dynamics. By comparison with other carotenoids, we show that a keto group at the acyloxy tail, even though it is not in conjugation, affects the electron distribution along the conjugated backbone, resulting in the observed decrease of the ICT character of the S1/ICT state of bFx and hFx.

• MeSH
• molekulární konformace MeSH
• simulace molekulární dynamiky * MeSH
• xanthofyly chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• fucoxanthin MeSH Prohlížeč
• xanthofyly MeSH

RC-LH1-PufX complexes from a genetically modified strain of Rhodobacter sphaeroides that accumulates carotenoids with very long conjugation were studied by ultrafast transient absorption spectroscopy. The complexes predominantly bind the carotenoid diketospirilloxanthin, constituting about 75% of the total carotenoids, which has 13 conjugated C=C bonds, and the conjugation is further extended to two terminal keto groups. Excitation of diketospirilloxanthin in the RC-LH1-PufX complex demonstrates fully functional energy transfer from diketospirilloxanthin to BChl a in the LH1 antenna. As for other purple bacterial LH complexes having carotenoids with long conjugation, the main energy transfer route is via the S2-Qx pathway. However, in contrast to LH2 complexes binding diketospirilloxanthin, in RC-LH1-PufX we observe an additional, minor energy transfer pathway associated with the S1 state of diketospirilloxanthin. By comparing the spectral properties of the S1 state of diketospirilloxanthin in solution, in LH2, and in RC-LH1-PufX, we propose that the carotenoid-binding site in RC-LH1-PufX activates the ICT state of diketospirilloxanthin, resulting in the opening of a minor S1/ICT-mediated energy transfer channel.

• Klíčová slova
• Carotenoids, Energy transfer, Intramolecular charge transfer state, Light-harvesting, Purple bacteria, Ultrafast spectroscopy,
• MeSH
• bakteriochlorofyly metabolismus   MeSH
• fluorescenční spektrometrie MeSH
• karotenoidy metabolismus   MeSH
• kinetika MeSH
• počítačové zpracování signálu MeSH
• přenos energie * MeSH
• Rhodobacter sphaeroides metabolismus   MeSH
• světlosběrné proteinové komplexy metabolismus   MeSH
• vysokoúčinná kapalinová chromatografie MeSH
• xanthofyly metabolismus   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• bakteriochlorofyly MeSH
• karotenoidy MeSH
• spirilloxanthin MeSH Prohlížeč
• světlosběrné proteinové komplexy MeSH
• xanthofyly MeSH

Violaxanthin-chlorophyll a protein (VCP) from Nannochloropsis oceanica is a Chl a-only member of the LHC family of light-harvesting proteins. VCP binds carotenoids violaxanthin (Vio), vaucheriaxanthin (Vau), and vaucheriaxanthin-ester (Vau-ester). Here we report on energy transfer pathways in the VCP complex. The overall carotenoid-to-Chla energy transfer has efficiency over 90%. Based on their energy transfer properties, the carotenoids in VCP can be divided into two groups; blue carotenoids with the lowest energy absorption band around 480nm and red carotenoids with absorption extended up to 530nm. Both carotenoid groups transfer energy efficiently from their S2 states, reaching efficiencies of ~70% (blue) and ~60% (red). The S1 pathway, however, is efficient only for the red carotenoid pool for which two S1 routes characterized by 0.33 and 2.4ps time constants were identified. For the blue carotenoids the S1-mediated pathway is represented only by a minor route likely involving a hot S1 state. The relaxed S1 state of blue carotenoids decays to the ground state within 21ps. Presence of a fraction of non-transferring red carotenoids with the S1 lifetime of 13ps indicates some specific carotenoid-protein interaction that must shorten the intrinsic S1 lifetime of Vio and/or Vau whose S1 lifetimes in methanol are 26 and 29ps, respectively. The VCP complex from N. oceanica is the first example of a light-harvesting complex binding only non-carbonyl carotenoids with carotenoid-to-chlorophyll energy transfer efficiency over 90%.

• Klíčová slova
• Carotenoids, Energy transfer, Femtosecond spectroscopy, Light-harvesting complex, Violaxanthin,
• MeSH
• chlorofyl a MeSH
• chlorofyl chemie   MeSH
• karotenoidy chemie   MeSH
• mikrořasy metabolismus   MeSH
• přenos energie MeSH
• světlosběrné proteinové komplexy chemie   MeSH
• xanthofyly chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• chlorofyl a MeSH
• chlorofyl MeSH
• karotenoidy MeSH
• světlosběrné proteinové komplexy MeSH
• violaxanthin MeSH Prohlížeč
• xanthofyly MeSH

In order to estimate the possible structure of the unknown carbonyl carotenoid related to isofucoxanthin from Chromera velia denoted as isofucoxanthin-like carotenoid (Ifx-l), we employed steady-state and ultrafast time-resolved spectroscopic techniques to investigate spectroscopic properties of Ifx-l in various solvents. The results were compared with those measured for related carotenoids with known structure: fucoxanthin (Fx) and isofucoxanthin (Ifx). The experimental data were complemented by quantum chemistry calculations and molecular modeling. The data show that Ifx-l must have longer effective conjugation length than Ifx. Yet, the magnitude of polarity-dependent changes in Ifx-l is larger than for Ifx, suggesting significant differences in structure of these two carotenoids. The most interesting spectroscopic feature of Ifx-l is its response to solvent proticity. The transient absorption data show that (1) the magnitude of the ICT-like band of Ifx-l in acetonitrile is larger than in methanol and (2) the S1/ICT lifetime of Ifx-l in acetonitrile, 4 ps, is markedly shorter than in methanol (10 ps). This is opposite behavior than for Fx and Ifx whose S1/ICT lifetimes are always shorter in protic solvent methanol (20 and 13 ps) than in aprotic acetonitrile (30 and 17 ps). Comparison with other carbonyl carotenoids reported earlier showed that proticity response of Ifx-l is consistent with presence of a conjugated lactone ring. Combining the experimental data and quantum chemistry calculations, we estimated a possible structure of Ifx-l.

• MeSH
• Alveolata chemie   MeSH
• karotenoidy chemie   MeSH
• rozpouštědla chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• karotenoidy MeSH
• rozpouštědla MeSH

The structure of 3-iodobenzaldehyde (3IB) was characterized by FT-IR, Raman and single-crystal X-ray diffraction techniques. The conformational isomers, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of 3IB were examined using density functional theory (DFT) method, with the Becke-3-Lee-Yang-Parr (B3LYP) functional and the 6-311+G(3df,p) basis set for all atoms except for iodine. The LANL2DZ effective core basis set was used for iodine. Potential energy distribution (PED) analysis of normal modes was performed to identify characteristic frequencies. 3IB crystallizes in monoclinic space group P21/c with the O-trans form. There is a good agreement between the theoretically predicted structural parameters, and vibrational frequencies and those obtained experimentally. In order to understand halogen effect, 3-halogenobenzaldehyde [XC6H4CHO; X=F, Cl and Br] was also studied theoretically. The free energy difference between the isomers is small but the rotational barrier is about 8kcal/mol. An atypical behavior of fluorine affecting conformational preference is observed.

• Klíčová slova
• 3-Halogenobenzaldehyde, Crystal structure, DFT, Vibrational spectra, XRD,
• MeSH
• benzaldehydy chemie   MeSH
• difrakce rentgenového záření * MeSH
• krystalografie rentgenová MeSH
• kvantová teorie * MeSH
• molekulární konformace MeSH
• molekulární modely * MeSH
• pravděpodobnost MeSH
• Ramanova spektroskopie * MeSH
• spektroskopie infračervená s Fourierovou transformací MeSH
• termodynamika MeSH
• vibrace MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• benzaldehyde MeSH Prohlížeč
• benzaldehydy MeSH

Two carotenoids with aryl rings were studied by femtosecond transient absorption spectroscopy and theoretical computational methods, and the results were compared with those obtained from their nonaryl counterpart, β-carotene. Although isorenieratene has more conjugated C═C bonds than β-carotene, its effective conjugation length, Neff, is shorter than of β-carotene. This is evidenced by a longer S1 lifetime and higher S1 energy of isorenieratene compared to the values for β-carotene. On the other hand, although isorenieratene and renierapurpurin have the same π-electron conjugated chain structure, Neff is different for these two carotenoids. The S1 lifetime of renierapurpurin is shorter than that of isorenieratene, indicating a longer Neff for renierapurpurin. This conclusion is also consistent with a lower S1 energy of renierapurpurin compared to those of the other carotenoids. Density functional theory (DFT) was used to calculate equilibrium geometries of ground and excited states of all studied carotenoids. The terminal ring torsion in the ground state of isorenieratene (41°) is very close to that of β-carotene (45°), but equilibration of the bond lengths within the aryl rings indicates that the each aryl ring forms its own conjugated system. This results in partial detachment of the aryl rings from the overall conjugation making Neff of isorenieratene shorter than that of β-carotene. The different position of the methyl group at the aryl ring of renierapurpurin diminishes the aryl ring torsion to ∼20°. This planarization results in a longer Neff than that of isorenieratene, rationalizing the observed differences in spectroscopic properties.

• MeSH
• karotenoidy chemie   klasifikace   MeSH
• molekulární struktura MeSH
• spektrofotometrie * MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Research Support, U.S. Gov't, Non-P.H.S. MeSH
• Názvy látek
• karotenoidy MeSH

We report on energy transfer pathways in the main light-harvesting complex of photosynthetic relative of apicomplexan parasites, Chromera velia. This complex, denoted CLH, belongs to the family of FCP proteins and contains chlorophyll (Chl) a, violaxanthin, and the so far unidentified carbonyl carotenoid related to isofucoxanthin. The overall carotenoid-to-Chl-a energy transfer exhibits efficiency over 90% which is the largest among the FCP-like proteins studied so far. Three spectroscopically different isofucoxanthin-like molecules were identified in CLH, each having slightly different energy transfer efficiency that increases from isofucoxanthin-like molecules absorbing in the blue part of the spectrum to those absorbing in the reddest part of spectrum. Part of the energy transfer from carotenoids proceeds via the ultrafast S2 channel of both the violaxanthin and isofucoxanthin-like carotenoid, but major energy transfer pathway proceeds via the S1/ICT state of the isofucoxanthin-like carotenoid. Two S1/ICT-mediated channels characterized by time constants of ~0.5 and ~4ps were found. For the isofucoxanthin-like carotenoid excited at 480nm the slower channel dominates, while those excited at 540nm employs predominantly the fast 0.5ps channel. Comparing these data with the excited-state properties of the isofucoxanthin-like carotenoid in solution we conclude that, contrary to other members of the FCP family employing carbonyl carotenoids, CLH complex suppresses the charge transfer character of the S1/ICT state of the isofucoxanthin-like carotenoid to achieve the high carotenoid-to-Chl-a energy transfer efficiency.

• Klíčová slova
• Apicomplexa, Carbonyl carotenoids, Energy transfer, FCP, Light-harvesting,
• MeSH
• Alveolata metabolismus   MeSH
• chlorofyl a MeSH
• chlorofyl metabolismus   MeSH
• fluorescenční spektrometrie MeSH
• karotenoidy metabolismus   MeSH
• přenos energie * MeSH
• světlosběrné proteinové komplexy metabolismus   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• chlorofyl a MeSH
• chlorofyl MeSH
• karotenoidy MeSH
• světlosběrné proteinové komplexy MeSH

Infrared and Raman spectra of 1-acetylpiperazine (1-ap) have been recorded in the region of 4000-40cm(-1). The conformational isomers, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of 1-ap (C6H12N2O) have been examined by density functional theory (DFT), with the Becke-3-Lee-Yang-Parr (B3LYP) functional and the 6-31++G(d,p) basis set. Reliable conformational investigation and vibrational assignments have been performed by the potential energy surface (PES) and potential energy distribution (PED) analyses, respectively. Computations are carried out in both gas phase and solution using benzene and methanol. There is a good agreement between the theoretically predicted structural parameters and vibrational frequencies and those obtained experimentally. The normal chair conformation with equatorial substituents is not preferred due to the steric interaction.

• Klíčová slova
• 1-Acetylpiperazine, DFT, PED, PES, Vibrational spectra,
• MeSH
• chemické modely * MeSH
• molekulární konformace * MeSH
• piperaziny chemie   MeSH
• počítačová simulace * MeSH
• Ramanova spektroskopie MeSH
• spektrofotometrie infračervená MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• piperaziny MeSH