Bacillus amyloliquefaciens AK-12 Helps Rapeseed Establish a Protection against Brevicoryne brassicae.

Aphids are a serious threat to rapeseed (Brassica napus L.) production, and cause unmanageable loss. Therefore, effective prevention and management strategies are urgently required to avoid losses. Bacillus amyloliquefaciens AK-12 isolated from a dead aphid with aphicidal activity was tagged with a green fluorescent protein through a natural transformation. The transformed strains were checked for stability and growth, and the best-performing strain was tested for its colonization inside and outside the rapeseed plant. The stability of AK-12-GFP reached more than 95%, and the growth curve was consistent with that of AK-12. After 30 days of treatment, the colonization of 1 × 106 CFU/g was recorded in rapeseed leaves. Interestingly, AK-12 reduced the aphid transmission rate compared with the control and improved the growth of the rapeseed seedlings. Meanwhile, the AK-12 strain also exhibited phosphorus, potassium-solubilizing, and nitrogen-fixing activity, and produced 2.61 µg/mL of IAA at 24 h. Regulation in the activity of four enzymes was detected after the AK-12 treatment. Phenylalanine ammonia lyase (PAL) was recorded at a maximum of 86.84 U/g after 36 h, and catalase (CAT) decreased after 48 h; however, peroxidase (POD) and polyphenol oxidase (PPO) reached the maximum within 12 h of AK-12 application. Additionally, important resistance genes related to these enzymes were upregulated, indicating the activation of a defense response in the rapeseed against aphids. In conclusion, defense enzymes and defense-related gene activation could improve the pest resistance in rapeseed, which has good application prospects for the future to be developed into biopesticide.

Fused perylenebisimide-carbazole: new ladder chromophores with enhanced third-order nonlinear optical activities.

A series of ladder chromophores featuring planar structures of fused perylenebisimide and carbazole have been efficiently synthesized via photocyclization under sun light. Compared to N,N'-bis(3-pentyl) perylenebisimide (PBI-1), they show remarkably enhanced nonlinear properties.

Starburst triarylamine donor-acceptor-donor quadrupolar derivatives based on cyano-substituted diphenylaminestyrylbenzene: tunable aggregation-induced emission colors and large two-photon absorption cross sections.

In this work, we have developed a new class of aggregation-induced emission (AIE) active compounds, in which three electron-donating diphenylamine, phenothiazine, or carbazole groups are connected to the 1, 4-positions of the benzene through bis(α-cyano-4-diphenylaminostyryl) conjugation bridges to form three triarylamine quadrupolar derivatives (3 a-c). Their one- and two-photon absorption properties have been investigated. The two-photon absorption (2PA) cross sections measured by the open-aperture Z-scan technique were determined to be 1016, 1484, and 814 GM for 3 a-c, respectively. From this result, the high 2PA properties of these molecules are attributed to the extended π system and enhanced intramolecular charge transfer from the starburst triarylamine to the cyano group. Moreover, cyano-substituted diphenylamine styrylbenzene (CNDPASB)-based compounds are very weakly fluorescent in THF, but their intensities increase by almost 230, 70, and 5 times, respectively, in water/THF (v/v 90 %) mixtures, in which they exhibit strongly enhanced red, orange, and deep yellow fluorescence emissions, respectively. This result indicates that the intramolecular vibration and rotation of these dyes is considerably restricted in nano-aggregates formed in water, leading to significant increases in fluorescence. It was found that the color tuning of the CNDPASB-based compounds could be conveniently accomplished by changing the starburst triarylamine donor moiety. Multilayer electroluminescence devices with TPBI (2,2',2''-(benzene-1,3,5-triyl)-tri(1-phenyl-1H-benzimidazole)) electron-transporting layers have been made, with 3 a and 3 c as a non-doping red-yellow emitter. The preliminary results for these multilayer devices show a maximum efficiency of 0.25 %, and electroluminescence (EL) wavelengths around 568 nm. The excellent 2PA and AIE properties of these compounds make them potential materials for biophotonic applications.

Synthesis, two-photon absorption and optical limiting properties of multi-branched styryl derivatives based on 1,3,5-triazine.

Five new multi-branched two-photon absorption triazine chromophores (T1-T5) with different donor strength, conjugation length, and direction of charge transfer have been designed and synthesized. The one-photon fluorescence, fluorescence quantum yields, and two-photon properties have been investigated. The two-photon absorption (2PA) cross sections measured by the open aperture Z-scan technique were determined to be 447, 854, 1023, 603, and 766 GM for T1, T2, T3, T4, and T5, respectively. This result indicates that their 2PA cross section values (σ) increase with increasing electron-donating strength of the end group, extending the conjugation length of the system, and introducing electron-withdrawing perfluoroalkyl as side groups to the end donor. In addition, the σ value of T5 is also larger than that of T1, which provides evidence that the σ value is relative to the direction of charge transfer (from the ends to the center of the molecule or from the center to the ends). Moreover, significant enhancement of the two-photon absorption cross section was achieved by introducing a thiophene moiety to a conjugated C==C bond. At the same time, the optical limiting behavior for these chromophores was studied by using a focused 800 nm laser beam with pulses of 140 fs duration. It was found that these molecules also exhibit good optical limiting properties. These initial results clearly demonstrate that multi-branched triazine chromophores are a highly suitable class of two-photon absorbing materials.

Star-shaped donor-pi-acceptor conjugated oligomers with 1,3,5-triazine cores: convergent synthesis and multifunctional properties.

Monodispersed oligomers have been widely developed and used in different optoelectronic areas due to their well-defined molecular structures, high purity, and solution processability. Star-shaped oligomers are especially interesting for OLED application because of their antiaggregation abilities and stable electroluminescence. In addition, star-shaped donor-pi-acceptor conjugated molecules are known to afford good nonlinear optical and two-photon absorption properties due to the intramolecular charge transfer and cooperative enhancement effects. In this context, three generations of highly soluble 1,3,5-triazine based donor-pi-acceptor compounds, TFT1, TFT2, and TFT3, were prepared through a convergent synthetic strategy and their optoelectronic properties were fully studied, which showed distinct correlations with the structures. Closed-aperture and open-aperture Z-scan methods were employed to measure the nonlinear refractive index and two-photon absorption properties of the oligomers, respectively. TFT1 showed a high nonlinear refractive index of 4.14 x 10(-12) esu in THF solution with an excitation wavelength of 800 nm. Also, TFT1 exhibited a large two-photon absorption cross section of 234 GM and a frequency up-converted two-photon excited fluorescence with a lambda(TPEF)(max) value of 527 nm under 800 nm laser irradiation with a pulse duration of 140 fs. OLED devices using the spin-coated films of these oligomers as an active layer showed intensive blue electroluminescence with a maximum luminance of 3093 cd/m(2) at a current efficiency of 1.47 cd/A from TFT1.

Multibranched triarylamine end-capped triazines with aggregation-induced emission and large two-photon absorption cross-sections.

Multibranched triarylamine derivatives with a 1,3,5-triazine core have been synthesized and exhibit aggregation-induced emission and a large two-photon absorption cross section (8629 GM).

Metal sulfide coated multiwalled carbon nanotubes synthesized by an in situ method and their optical limiting properties.

A metal sulfide such as ZnS, CdS, Ag(2)S or PbS was coated on the sidewall of multiwalled carbon nanotubes (MWCNTs) by an in situ wet chemical synthesis approach via noncovalent functionalization of MWCNTs with a polyelectrolyte (polyethylenimine or poly(diallyldimethylammonium chloride)) without causing significant electronic and structural modification of the carbon nanotubes. Extensive characterizations of the fabricated nanocomposites have been performed using x-ray diffraction, transmission electron microscopy (TEM), high resolution TEM, energy dispersive x-ray spectroscopy, selected area electron diffraction, thermal gravimetric analysis, Fourier transform IR spectra, UV-vis spectra and x-ray photoelectron spectroscopy. The coating layers were composed of metal sulfide nanoparticles with a mean size of less than 10 nm. The optical limiting property measurements for some metal sulfide coated MWCNTs were carried out by the open-aperture z-scan technique. The results demonstrate that the samples suspended in water showed optical limiting behavior better than that of purified MWCNTs.

[Study on absorption spectra and optical limiting properties of soluble polymer/multi-walled carbon nanotube composites].

Three kinds of soluble polymer grafted multi-walled carbon nanotubes (MWNTs), including poly(N-vinylcarbazole)-MWNTs (MWNTs-PVK), polystyrene-MWNTs (MWNTs-PSt) and poly(methyl methacrylate)-MWNTs (MWNTs-PMMA) were synthesized. The TEM images of these samples show that polymers are coated outside the carbon nanotubes. The UV-Vis absorption spectra of the samples in CHCl3 were taken on a HP8452 spectrophotometer at room temperature. Compared with that of MWNTs suspension, there is a characteristic absorption peak in the ultraviolet region, which can be attributed to the polymers linked covalently with MWNTs. Their nonlinear optical properties and optical limiting (OL) performances were investigated by Z-scan method with 527 nm nanosecond laser pulses. These MWNTs dissolved in chloroform possess similar optical limiting properties, which are better than that of raw MWNT suspension and C60 in toluene solution. Nonlinear refraction, nonlinear absorption and nonlinear scattering mechanism were taken into consideration for explaining the observed results. The analysis of the experimental results shows that nonlinear absorption is the dominant mechanism behind the OL performance of these samples.

Enhanced two-photon absorption and ultrafast dynamics of a new multibranched chromophore with a dibenzothiophene core.

A series of novel compounds with dibenzothiophene core branched structures have been synthesized, and their two-photon absorption (TPA) properties were investigated. Two-photon fluorescence (TPF) and z-scan techniques were carried out, and a significant enhancement in the TPA cross section was observed for ST-G2, which possesses the largest generation number among the studied samples. By using different solvents, the largest nonlinear optical (NLO) response was observed in the most polar solvent. Ultrafast pump-probe experiments were performed to probe the excited state dynamics in the branched molecules, and the obtained results further confirmed the TPA enhancement mechanism. Time-resolved fluorescence (TRFL) and TRFL anisotropy measurements reveal that there is an ultrafast charge localization to the intramolecular charge transfer (ICT) state followed by relaxation with a lifetime longer than 1 ns.

[Transient dynamics of excited states and nonlinear optical properties of InP nanoparticles].

The decay curves of the emission at different wavelength were measured. One nanosecond of transition lifetime of interband was obtained. The transient dynamics of InP nanoparticles was investigated by one color femtosecond pump-probe method at the wavelength of 800 nm. The experimental result shows that the saturation of exciton resonance results in photobleaching at 800 nm The decay process of the bleaching includes two components, i.e. the fast one from free carries scattering and the slow one from trapped carriers scattering. The nonlinear optical properties of InP nanoparticles were investigated by using femtosecond optical Kerr effect. The magnitude of chi3 for InP nanoparticles embedded in SiO2 sol-gel glass was calculated, and its origin was analyzed.

Ultrafast excited state dynamics of modified phthalocyanines: p-HPcZn and p-HPcCo.

Two modified metallophthalocyanines (MPcs) containing sulfonic naphthoxy substituents were synthesized. The measurements of transient absorption and time-resolved photoluminescence were used to study the ultrafast response and excited state dynamics of two MPcs in dimethyl sulfoxide (DMSO) solution, which were predominantly in the monomeric form. Under excitation at 400 nm, these molecules experience vibrational relaxation to the bottom of the first excited state and then the excitation rapidly converts to the low-lying charge-transfer (CT) state and finally reaches the triplet states. Under excitation at 800 nm, they show a two-photon absorption character, and their excited state dynamics exhibit strong dependence on the probe wavelength. The main results with 400 nm pumping are similar to the results with 800 nm pumping. For p-HPcZn, weak two-photon photoluminescence was also observed with a lifetime of 52 +/- 2 ps. A four-level model was used to illustrate the excited state dynamics of p-HPcZn, while a five-level model was suggested for p-HPcCo molecule.

The observation of ultrafast excited-state dynamical evolution in B800- partially or completely released LH2 of Rhodobacter sphaeroides 601 at room temperature.

Photodynamics of two kinds of peripheral antenna complexes (LH2 of Rhodobacter sphaeroides, native LH2 (RS601) and B800-released LH2 where B800-BChls were partially or completely removed with different pH treatments), were studied using femtosecond pump-probe technique at different laser wavelengths. The obtained results for these samples with different B800/B850 ratios demonstrated that under the excitation around B800 nm, the photoabsorption and photobleaching dynamics were caused by the direct excitation of upper excitonic levels of B850 and excited state of B800 pigments, respectively. Furthermore, the removal of B800 pigments had little effect on the energy transfer processes of B850 interband/intraband transfer.

Effect of the in situ electrochemical oxidation on the pigment-protein arrangement and energy transfer in light-harvesting complex from Rhodobacter sphaeroides 601.

The oxidation of bacteriochlorophylls (BChls) in peripheral light-harvesting complexes (LH2) from Rhodobacter sphaeroides was investigated by spectroelectrochemistry of absorption, fluorescence emission, and femtosecond (fs) pump-probe, with the aim obtaining information about the effect of in situ electrochemical oxidation on the pigment-protein arrangement and energy transfer within LH2. The experimental results revealed that: (a) the generation of the BChl radical cation in both B800 and B850 rings dramatically induced bleaching of the characteristic absorption in the NIR region and quenching of the fluorescence emission from the B850 ring for the electrochemical oxidized LH2; (b) the BChl-B850 radical cation might act as an additional channel to compete with the unoxidized BChl-B850 molecules for rapidly releasing the excitation energy, however the B800-B850 energy transfer rate remained almost unchanged during the oxidation process.

The ultrafast dynamics and nonlinear optical properties of tribranched styryl derivatives based on 1,3,5-triazine.

By using the femtosecond laser spectroscopic techniques, we have studied the ultrafast response and the nonlinear optical properties of three molecules with donor-acceptor structure (denoted as T01, T02, and T03). Two-photon absorption (2PA) cross sections measured by the open aperture Z-scan technique were determined to be 77, 90, and 410 GM for T01, T02, and T03, respectively. The relaxation dynamics of the excited states were measured by two-color femtosecond pump-probe and time-resolved photoluminescence (PL) experiments. By changing the solvent from chloroform (CHCl3) to dimethyl sulfoxide (DMSO), the transient dynamics was found changed significantly and the decay time of PL emission decreased dramatically because DMSO with large dipole moment accelerates the cross-transfer process and the nonradiative process in the molecules.

Annealing effect of linear and nonlinear optical properties of Ag:Bi2O3 nanocomposite films.

Silver nanoparticle/bismuth oxide composite films were deposited by cosputtering and annealed at different temperatures. The X-ray diffraction results demonstrate that the silver and bismuth oxide were well crystallized after 600 degrees C thermal annealing. The linear absorption peaks show a red-shift behavior while increasing annealing temperature. The annealing effect of the third-order nonlinear optical susceptibilities and ultrafast nonlinear optical response of the silver nanoparticles/bismuth oxide composite thin films are investigated using the femtosecond time-resolved optical Kerr effect technique under 800 nm wavelength. The maximum value of chi(3) of Ag:Bi2O3 thin films is 2.1X10 esu, which occurs at an annealing temperature of 600 degrees C. The ultrafast optical response spectra demonstrate the temperature dependence of decay process time.

Dynamics of primary events in the photocycle of excited bacteriorhodopsin.

Transient dynamic behavior of the excited bacteriorhodopsin (BR), which was isolated from the strain H. salinarum, was studied at excitation wavelength from 585 to 639 nm. With the one-color femtosecond (fs) pump-probe technique, we revealed the primary events in BR's photocycle that took place in an ultrafast time scale. From the analysis of the decay components of the dynamical traces, it was evident that the isomerization of the retinal chromophore in BR and the intermediate J's formation occurred within 500 fs. BR exhibited pH-dependent dynamical behaviors. When the medium pH was between 5 and 9, the BR ultrafast dynamics has no obvious change. In contrast, the dynamical curves were obviously affected when the pH was out of that region.

Excitation relaxation in the chemically modified photosynthetic reaction center from Rhodobacter sphaeroides 601.

The ultrafast excitation relaxation in the sodium borohydride-treated reaction center of Rhodobacter sphaeroides 601 was investigated with selective excitation. From the femtosecond pump-probe measurement at 790 nm, the excitation relaxation demonstrates a biexponential decay with time constants of about 200 fs and 1.4 ps. By comparison with the result from sodium ascorbate-pretreated modified RS601, it could be concluded that the dynamical trace at 790 nm mainly originates from the contribution of accessory bacteriochlorophyll in the active side, and the electrochromic shift arising from the induced positive charge on the special pair primarily affects the absorption band in the red region of the accessory bacteriochlorophyll in RS601. With direct excitation of the special pair, the charge separation and subsequent electron transfer were observed in borohydride-modified RS601. The 2.8 ps component was ascribed to the charge separation and electron transfer from P* to H(A). From the dynamical traces at 790, 800 and 818 nm, the ultrafast energy relaxation from the excited accessory bacteriochlorophyll in the active side is consistent with a two-step energy transfer mechanism. This dynamical observation in modified RS601 is of significance in understanding the physical mechanism of excitation relaxation and energy transfer in the photosynthetic primary process.

The observation of excited-state dynamical evolution in light-harvesting complex LH2 from Rhodobacter sphaeroides 601.

With selective excitation around BChl-B800 and BChl-B850 absorption bands, we observed the evolution of excited-state dynamics in LH2 from Rhodobacter sphaeroides 601. The dynamical traces demonstrate a dominant excited-state absorption (ESA) followed concomitantly by an ultrafast transmission increase and decay with pulse-width limited time scale at 818 nm and 828 nm excitation. The ESA occurring prior to excitonic thermalization or ground-state bleach was observed at 840 nm as well. These experimental results indicate the competition between the transition from excitonic states to higher-lying excited states and interexciton relaxation, which are of physical significance for understanding excitation transfer and related mechanisms in LH2.

Size and dielectric dependence of the third-order nonlinear optical response of Au nanocrystals embedded in matrices.

The third-order nonlinear optical response of Au nanocrystals embedded in BaTiO(3) and ZrO(2) matrices was investigated through the off-resonance femtosecond optical Kerr effect. Compared with pristine films, the nonlinearity of composite films shows an enhancement that depends on the sizes of Au particles and the refractive index of the matrices. We performed a calculation based on Lorenz-Mie scattering theory to explain the experimental results. Additionally, the nonlinearity was optimized by determination of the values of the particle size and the refractive index of the matrix.

[The charge transfer process of PAN-C60 copolymer films by time-resolved fluorescence spectra].

The charge transfer (CT) process in PAN-C60 copolymer films was studied by absorption and picosecond time-resolved photoluminescence (TRPL) spectra. The CT process can be confirmed from the appearing of new absorption bands and fluorescence quenching of pure PAN in the copolymer films. The TRPL result revealed that excitation state relaxation obeyed biexponential decay process, which were 160 ps and 1,500 ps for the fast and slow decay process, respectively. The fast decay process results from the interaction of chains in the polymer, and a slow decay process comes from the singlet excition recombination. In the copolymer, the singlet excition state lifetime of PAN becomes shorter due to CT process between PAN and C60, which lead to PL quenching of PAN. Additionally, C60 molecules also affect the interchain interaction of PAN by its spacial shape, which closely relates with the fast decay process.