Factorial Design to Optimize Dextran Production by the Native Strain Leuconostoc mesenteroides SF3.

Dextran is an extracellular bacterial polysaccharide for which industrial applications have been found in different areas. Several researchers have optimized the fermentation conditions to maximize dextran production. This study aimed to characterize the dextran of Leuconostoc mesenteroides SF3, which was isolated from the aguamiel of Agave salmiana. To maximize the yield of dextran, the effects of sucrose concentration, temperature, and incubation time were studied. The experiments were conducted using a factorial design and a response surface methodology. L. mesenteroides SF3 produced a maximum yield of dextran (23.8 g/L ± 4) after 16 h of incubation at 25 °C with 10% sucrose. The functional properties such as water absorption capacity, oil absorption capacity, and emulsion activity of this unique dextran were 361.8% ± 3.1, 212.0% ± 6.7, and 58.3% ± 0.7, respectively. These properties indicate that the dextran produced by L. mesenteroides SF3 is a high-quality polysaccharide with potential applications in the food industry, and the optimized conditions for its production could be used for the commercial production of this dextran, which have significant industrial perspectives.

Experimental and computational data on two-photon absorption and spectral deconvolution of the upper excited states of dye IR780.

Evaluating candidates for novel materials with high nonlinear absorption properties for applications as biomarkers is a very important field of research. In this context, experimental and computational information on the two-photon absorption (TPA) properties of the dye IR780 is shown. The two-photon absorption data from 850 to 1000 nm for IR780 and other two well-known dyes, taken as reference, are presented. The experimental data were collected via an implementation of the two-photon induced fluorescence technique, while the quantum chemical data were produced by implementing DFT (Density-functional theory) methods. The data presented here supplement the paper "Two-photon absorption spectrum and characterization of the upper electronic states of dye IR780" by Guarin et al. (2021).

Two-photon absorption spectrum and characterization of the upper electronic states of the dye IR780.

In this work, the full two-photon absorption (2PA) spectrum of cyanine dye IR780 in methanol was measured and some important properties of the upper excited electronic states were investigated. Specifically, two IR780 2PA bands of intensities nearing 140 and 2800 Goeppert-Mayer (GM) were found. In order to determine the optical properties of the upper electronic singlet states, a deconvolution of the absorption peaks in the UV region of the spectrum was made. Based on this, properties such as transition dipole moments, oscillator strengths, absorption maxima in the UV-vis spectra, S2-S1 vibrational couplings and predictions of the lifetime of the second excited state were calculated. Moreover, by combining experimental and computational results, the 2PA transitions were assigned to the upper excited states S2 and S4. Cross-section magnitudes, positions and shapes of the 2PA bands have been satisfactorily explained with a four-state model that comprises the singlet states S1, S2 and S4. From these results, the cyanine investigated in the present work could be used as a novel and interesting moiety for more complex systems that respond to two-photon excitation.

Linear and Nonlinear Optical Properties of Functional Groups for Conjugated Polymers. Analysis of the Acceptor-Donor Pair Substituents of Benzene: The Case of meta-Nitroaniline.

The nonlinear optical (NLO) properties of meta-nitroaniline (m-NA) are evaluated via Hückel-Agrawal's approximation in a solvent environment. In this context, both the 1B and the intramolecular charge transfer (ICT) electronic transitions are considered. The benzene ring currents on the clockwise or counterclockwise direction and the corresponding Brillouin zone from 0 to π are also considered. Besides, the Bloch equations were applied to a single cell n = 1 defined on the benzene ring. We have considered that the light beam was directed along the ring benzene bonds of m-NA; this topological hypothesis changed the crystal structure to a linear chain and the calculated optical properties were found near the experimental ones. In addition, the Fermi's golden rule was applied to the crystal state and then the calculated refraction index of m-NA had an error of less than 3% of the experimental one. On the other hand, the molar absorptivity ε of m-NA in acetonitrile for the 1B and intramolecular ICT transitions was experimentally determined to be 11 981 and 1192 L mol-1 cm-1, respectively. With this methodology, we found that the change of the charge in the NO2 group has also a strong influence on the linear and NLO properties. In addition, the dipole transition moments, which are originated from the carbon between the carbons joined to NO2 and NH2, are mainly involved in the NLO properties. Thus, the first hyperpolarizability ß z was 1.69 × 10-30 esu at λLaser = 1064 nm, 27% of the experimental value. We attribute this difference to the evaluation of the excited dipole moment. If we attribute a separation of charge of 0.1 e in the excited state, the new dipole moment allows for the simulation of the experimental value. Besides, the calculated value of χ(3) for m-NA in a solution of acetonitrile is 2.9 × 10-13 esu at λLaser = 1064 nm, 158% of the experimental value. The discrepancy between these values is attributed to the influence of the electronic correlation effects, that is, because of resonance structures of the aromatic ring and the zwitterionic pair of nitro and aniline. Besides, we have also evaluated the second hyperpolarizability γ, the second-order susceptibility χ(2) of m-NA and their values have similar differences to the experimental values. This type of approach is important because it reduces computing time and gives insight into the molecular causes responsible for linear and NLO properties in this type of functional groups, which can be used as building blocks in more complex polymer systems.

Dynamics of the formation of a charge transfer state in 1,2-bis(9-anthryl)acetylene in polar solvents: symmetry reduction with the participation of an intramolecular torsional coordinate.

We have studied 1,2-bis(9-anthryl)acetylene as a model compound for the characterization of the process of solvent-mediated symmetry reduction in an excited state. Thanks to the acetylenic bridge that joins the two anthracenic moieties, this system maintains minimal steric hindrance between the end chromophores in comparison with the classic 9,9'-bianthryl model compound. The acetylenic bridge also allows for significant electronic coupling across the molecule, which permits a redistribution of electron density after light absorption. Femtosecond resolved fluorescence measurements were used to determine the spectral evolution in acetonitrile and cyclohexane solutions. We observed that, for 1,2-bis(9-anthryl)acetylene, the formation of a charge transfer state occurs in a clear bimodal fashion with well separated time scales. Specifically, the evolution of the emission spectrum involves a first solvent-response mediated subpicosecond stage where the fluorescence changes from that typical of nonpolar solvents (locally excited) to an intermediate, partial charge transfer state. The second stage of the evolution into a full charge transfer state occurs with a much longer time constant of 37.3 ps. Since in this system the steric hindrance is minimized, this molecule can undergo much larger amplitude motions for the torsion between the two anthracenic moieties associated with the charge redistribution in comparison with the typical model compound 9,9'-bianthryl. Clearly, the larger range of motions of 1,2-bis(9-anthryl)acetylene gives the opportunity to study the electron transfer process with a good separation of the time scales for the formation of a partial charge transfer state, determined by the speed of solvent response, and the intramolecular changes associated with the formation of the fully equilibrated charge transfer state.

The influence of push-pull states on the ultrafast intersystem crossing in nitroaromatics.

The photochemistry of nitro-substituted polyaromatic compounds is generally determined by the rapid decay of its S1 state and the rapid population of its triplet manifold. Previous studies have shown that such an efficient channel is due to a strong coupling of the fluorescent state with specific upper receiver states in the triplet manifold. Here we examine variations in this mechanism through the comparison of the photophysics of 2-nitrofluorene with that of 2-diethylamino-7-nitrofluorene. The only difference between these two molecules is the presence of a diethylamino group in a push-pull configuration for the latter compound. The femtosecond-resolved experiments presented herein indicate that 2-nitrofluorene shows ultrafast intersystem crossing which depopulates the S1 emissive state within less than a picosecond. On the other hand, the amino substituted nitrofluorene shows a marked shift in its S1 energy redounding in the loss of coupling with the receiver triplet state, and therefore a much longer lifetime of 100 ps in cyclohexane. In polar solvents, the diethylamino substituted compound actually shows double peaked fluorescence due to the formation of charge transfer states. Evaluation of the Stokes shifts in different solvents indicates that both bands correspond to intramolecular charge transfer states in equilibrium which are formed in an ultrafast time scale from the original locally excited (LE) state. The present study addresses the interplay between electron-donating and nitro substituents, showing that the addition of the electron-donating amino group is able to change the coupling with the triplet states due to a stabilization of the first excited singlet state and the rapid formation of charge transfer states in polar solvents. We include calculations at the TD-DFT level of theory with the PBE0 and B3LYP functionals which nicely predict the observed difference between the two compounds, showing how the specific S(π-π*)-T(n-π*) coupling normally prevalent in nitroaromatics is lost in the push-pull compound.

Dynamics of the higher lying excited states of cyanine dyes. An ultrafast fluorescence study.

The electronic relaxation dynamics of the second singlet excited states of several cyanine dyes was studied through the femtosecond fluorescence up-conversion technique. Our interest in these molecules comes from the potential applications of systems with upper excited singlet states with a long lifetime, which can include electron and energy transfer from the higher lying singlets after one- or two-photon absorption. We studied three series of cyanines with 4-quinolyl, 2-quinolyl, or benzothiazolyl type end groups, each with varying sp(2) carbon conjugation lengths in the methinic bridge. The dynamics after electronic excitation to singlet states above the fluorescent state vary significantly as a function of cyanine structure and conjugation length. In particular, for the 4-quinolyl series the cyanine with an intermediate conjugation length (three methinic carbons) has the slowest S2 decays with lifetimes of 5.4 ps in ethanol and 6.6 ps in ethylene glycol. On the other hand, we observed that the 2-quinolyl family has S2 decay times in the subpicosecond range independent of the conjugation length between the end groups. The slowest internal conversion was observed for the benzothiazolyl type cyanine with five methinic carbons, with an S2 lifetime of 17.3 ps in ethanol. For the planar cyanines of this study we observed for the first time a clear systematic trend in the S2 decay times which closely follow the energy gap law. It was also demonstrated that a slow S2 decay is as well observed upon excitation through degenerate two-photon absorption with near-IR pulses. The present study isolates the most important variables for the design of cyanines with long S2 lifetimes.

Ultrafast photosensitization of phthalocyanines through their axial ligands.

We have studied the energy transfer properties of a novel silicon phthalocyanine that coordinates two anthracene-9-carboxylate groups in the form of trans axial ligands. Our objectives were to generate a system with auxiliary chromophores that enhance the light absorption properties of the macrocycle in a specific region in the UV and to evaluate the efficiency and time scales for energy transfer. The ligand coordination through a carboxylate group directly attached to the anthracenic system allows for close proximity of the donor and acceptor chromophores. The energy transfer process was observed to be nearly 100% efficient and to occur on a time scale of 370 fs. From the energy relations of the donor and acceptor states and the observed dynamics, the initial energy transfer step is likely to involve upper electronic states of the phthalocyanine rather than the states of the lowest-energy vibroelectronic Q bands.