Vibrational-Mode-Selective Modulation of Electronic Excitation.

Vibrational-mode-selective modulation of electronic excitation is conducted with a synchronized femtosecond (fs) visible (vis) pulse and a picosecond (ps) infrared (IR) pulse. The mechanism of modulation of vibrational and vibronic relaxation behavior of excited state is investigated with ultrafast vis/IR, IR/IR, and vis-IR/IR transient spectroscopy, optical gating experiments and theoretical calculations. An organic molecule, 4'-(N,N-dimethylamino)-3-methoxyflavone (DMA3MHF) is chosen as the model system. Upon 1608 cm-1 excitation, the skeleton stretching vibration of DMA3MHF is energized, which can significantly increase the Franck-Condon factor for electronic transition, facilitate the radiative decay and promote emission from vibrational excited states. As results, a remarkable enhancement and a slight blueshift in fluorescence are observed. The mode-selective modulation of electronic excitation is not limited in luminescence or photophysics. It is expected to be widely applicable in tuning many photochemical processes.

Blue-Shifted and Broadened Fluorescence Enhancement by Visible and Mode-Selective Infrared Double Excitations.

Mode-selective vibrational excitations to modify the electronic states of fluorescein dianion in methanol solutions are carried out with a femtosecond visible pulse synchronized with a tunable high-power, narrow-band picosecond infrared (IR) pulse. In this work, simultaneous intensity enhancement, peak blueshift, and line width broadening of fluorescence are observed in the visible/IR double resonance experiments. Comprehensive investigations on the modulation mechanism with scanning the vibrational excitation frequencies, tuning the time delay between the two excitation pulses, theoretical calculations, and nonlinear and linear spectroscopic measurements suggest that the fluorescence intensity enhancement is caused by the increase of the Franck-Condon factor induced by the vibrational excitations at the electronic ground state. Various enhancement effects are observed as vibrations initially excited by the IR photons relax to populate the vibrational modes of lower frequencies. The peak blueshift and line width broadening are caused by both increasing the Franck-Condon factors among different subensembles because of IR pre-excitation and the long-lived processes induced by the initial IR excitation. The results demonstrate that the fluorescence from the visible/IR double resonance experiments is not a simple sum frequency effect, and vibrational relaxations can produce profound effects modifying luminescence.

Staggered Assembly of a Dimeric Au13 Cluster: Impacts on Coupling of Geometric Isomerism.

The specific states of aggregation of metal atoms in sub-nanometer-sized gold clusters are related to the different quantum confinement volumes of electrons, leading to novel optical and electronic properties. These volumes can be tuned by changing the relative positions of the gold atoms to generate isomers. Studying the isomeric gold core and the electron coupling between the basic units is fundamentally important for nanoelectronic devices and luminescence; however, appropriate cases are lacking. In this study, the structure of the first staggered di-superatomic Au25 -S was solved using single-crystal X-ray diffraction. The optical properties of Au25 -S were studied by comparing with eclipsed Au25 -E. From Au25 -E to Au25 -S, changes in the electronic structures occurred, resulting in significantly different optical absorptions originating from the coupling between the two Au13 modules. Au25 -S shows a longer electron decay lifetime of 307.7 ps before populating the lowest triplet emissive state, compared to 1.29 ps for Au25 -E. The experimental and theoretical results show that variations in the geometric isomerism lead to distinct photophysical processes owing to isomerism-dependent electronic coupling. This study offers new insights into the connection between the geometric isomerism of nanosized building blocks and the optical properties of their assemblies, opening new possibilities for constructing function-specific nanomaterials.

Restriction of crossing conical intersections: the intrinsic mechanism of aggregation-induced emission.

Elucidating the mechanism of aggregation-induced emission (AIE) is a prerequisite for designing more AIE-gens. The diphenylethylene (DPE) featured molecules are one of the most important AIE-gens due to their propeller structure. Three representative DPE-featured AIE-gens, triphenylethylene, cis-stilbene, and trans-stilbene, are explored via ultrafast ultraviolet/infrared (UV/IR) spectroscopy and theoretical calculations. Both experimental and computational results suggest that readily crossing conical intersections (CIs) with flexible structural evolutions in solutions significantly reduces fluorescence, whereas crossing CIs is restricted because of high energy cost, and therefore no fast nonradiative decay can compete with spontaneous emission in solids. The mechanism also well explains the different emission quantum yields and interconversion ratios between cis-stilbene and trans-stilbene after photoexcitation.

Direct observation of conformations of a high-mobility n-type low-bandgap copolymer in solutions and solid films.

The aggregation morphologies of conjugated polymers in solutions and solid films are important for their optoelectronic applications. Due to the amorphous state of the polymers, it remains a great challenge to determine their conformations in either liquids or solids. Herein, a ps/fs synchronized 2D IR technique is applied to investigate the molecular conformations of a high-mobility n-type low-bandgap copolymer, N2200, dissolved in CHCl3 and CCl4, and in solid films cast from both solutions by the vibrational cross-angle method. In CCl4, the polymer forms more aggregates and folds more and the backbone dihedral angle of C-C(NDI)/C-S(Thiophene) of its average conformation is about 10° more distorted than that in CHCl3 and the most stable conformation for a free molecule. Anti-intuitively, the solid films cast from both solutions have the same molecular conformation, and the conformation is similar to that of the polar CHCl3 rather than the conformation of the less polar CCl4. The results imply that the interaction between the polymer backbones is probably stronger than its interaction with CCl4, which can naturally guide the rearrangement of polymer chains during the evaporation of solvent molecules. This work also implies that the balance and competition between the polymer/polymer interaction and the polymer/solvent interaction seem to be the dominant factors responsible for what morphology can form in a solid film cast from solution. It is not always true that different molecular conformations must exist in solid films grown from different solutions with different polarity or different extents of aggregates with different conformations.

Clonostachys rosea Promotes Root Growth in Tomato by Secreting Auxin Produced through the Tryptamine Pathway.

Clonostachys rosea (Link) Schroers is a filamentous fungus that has been widely used for biological control, biological fermentation, biodegradation and bioenergy. In this research, we investigated the impact of this fungus on root growth in tomato and the underlying mechanisms. The results showed that C. rosea can promote root growth in tomato, and tryptophan enhances its growth-promoting impacts. The results also showed that tryptophan increases the abundance of metabolites in C. rosea, with auxin (IAA) and auxin-related metabolites representing a majority of the highly abundant metabolites in the presence of tryptophan. It was noted that C. rosea could metabolize tryptophan into tryptamine (TRA) and indole-3-acetaldehyde (IAAId), and these two compounds are used by C. rosea to produce IAA through the tryptamine (TAM) pathway, which is one of the major pathways in tryptophan-dependent IAA biosynthesis. The IAA produced is used by C. rosea to promote root growth in tomato. To the best of our knowledge, this is the first report on IAA biosynthesis by C. rosea through the TAM pathway. More research is needed to understand the molecular mechanisms underlying IAA biosynthesis in C. rosea, as well as to examine the ability of this fungus to boost plant development in the field.

Double crossing conical intersections and anti-Vavilov fluorescence in tetraphenyl ethylene.

Conical intersections (CIs) provide effective fast nonradiative decay pathways for electronic excitation, which can significantly influence molecular photoluminescence properties. However, in many cases, crossing a CI does not have direct observables, making studies of CIs experimentally challenging. Herein, the theoretically predicted double CIs by cis-trans twisting and cyclization in tetraphenyl ethylene, a well-known aggregation-induced emission molecule, are investigated with excitation dependent ultrafast UV/IR spectroscopy and fluorescence. Both the fluorescence quantum yield and the efficiency of cyclization are found to be smaller with a shorter excitation wavelength. An abrupt change occurs at about 300-310 nm. The results imply that crossing the twisting CI has a larger barrier than the cyclization CI, and the cis-trans twisting motion is probably involved with large solvation reorganization.

Facile synthesis of core\shell Fe3O4@mSiO2(Hb) and its application for organic wastewater treatment.

Treatment of organic wastewater is a challenging task. Biological techniques using biocatalysts have shown their benefits in organic wastewater treatment. In this research, a novel biocatalyst was developed by encapsulation of Fe3O4 microspheres and haemoglobin (Hb) with mesoporous silica, named Fe3O4@mSiO2(Hb). Fe3O4@mSiO2(Hb) exhibited typical mesoporous characteristics (mesoporous silica), magnetic feature (Fe3O4) and peroxidase activity (Hb). The results showed that the immobilization of Hb into Fe3O4@mSiO2 did not affect its activity. In addition, Fe3O4@mSiO2(Hb) exhibited a higher efficiency in the peroxidation of aromatic compounds than free Hb. The peroxidase activity of the synthesized biocatalyst was estimated to be 120 Ug-1, which was almost four times greater than that of previously reported immobilized Hb. Also, the Km of Fe3O4@mSiO2(Hb) was similar to that of the free Hb and it was estimated to be 4.3 × 10-4 µM, indicating that the activity of the Hb in the immobilized enzyme was not affected after immobilization. The immobilized enzyme was also found to be stable, recyclable and reusable. Taken together, these results indicate that the Fe3O4@mSiO2(Hb) has good potential to be used for treating organic wastewater containing aromatic compounds. The magnetically separable novel biocatalyst developed in this study provided not only a more suitable microenvironment for retaining the activity of Hb, but also demonstrated enhanced stability and activity under unfavorable conditions.

Postharvest Treatments with Three Yeast Strains and Their Combinations to Control Botrytis cinerea of Snap Beans.

Three yeast strains, namely Cryptococcus albidus (Ca63), Cryptococcus albidus (Ca64), and Candida parapsilosis (Yett1006), and their combinations, including single yeast agent, two combined yeast strains, single yeast agent + NaHCO3, single yeast agent + chitosan, single yeast agent + ascorbic acid, and single yeast agent + konjac powder, were evaluated for their activity against Botrytis cinerea, the most economically important fungal pathogens causing postharvest disease of snap beans. In in vitro tests, no inhibition zone was observed in dual cultures of three yeast strains and B. cinerea. The mycelial growth inhibition rates of B. cinerea for Ca63, Ca64, and Yett1006 were 97%, 95%, and 97%, respectively. In in vivo tests, the optimal combination of the lowest disease index of snap beans with B. cinerea was Ca63 + Ca64, with a preventing effect of 75%. The decay rate and rust spots index of Ca64 + ascorbic acid combination were 25% and 20%, respectively, which were the lowest. The activities of defense-related enzymes increased, while malondialdehyde (MDA) content was suppressed in snap beans after different treatments. Our results highlight the potential of the three yeast strains and their combinations as new nonpolluting agents for the integrated control of B. cinerea on snap beans.

A Study of the Interaction, Morphology, and Structure in Trypsin-Epigallocatechin-3-Gallate Complexes.

Understanding the interaction between proteins and polyphenols is of significance to food industries. The aim of this research was to investigate the mode of aggregation for trypsin-EGCG (Epigallocatechin-3-gallate) complexes. For this, the complex was characterized by fluorescence spectroscopy, circular dichroism (CD) spectra, small-angel X-ray scattering (SAXS), and atomic force microscope (AFM) techniques. The results showed that the fluorescence intensity of trypsin-EGCG complexes decreased with increasing the concentration of EGCG, indicating that the interaction between trypsin and EGCG resulted in changes in the microenvironment around fluorescent amino acid residues. The results of CD analysis showed conformational changes in trypsin after binding with EGCG. The results from SAXS analysis showed that the addition of EGCG results in the formation of aggregates of trypsin-EGCG complexes, and increasing the concentration of EGCG resulted in larger aggregates. AFM images showed that the trypsin-EGCG complex formed aggregates of irregular ellipsoidal shapes with the size of about 200 × 400 × 200 nm, with EGCG interconnecting the trypsin particles. Overall, according to these results, it was concluded that the large aggregates of trypsin-EGCG complexes are formed from several small aggregates that are interconnected. The results of this study shed some light on the interaction between digestive enzymes and EGCG.

Comparative Genomic and Physiological Analyses of a Superoxide Dismutase Mimetic (SODm-123) for Its Ability to Respond to Oxidative Stress in Tomato Plants.

Superoxide dismutases (SODs) are a group of enzymes that have a crucial role in controlling oxidative stress in plants. Here, we synthesized an environmentally friendly SOD mimic, SODm-123, from L-aspartic acid and manganese oxide. SODm-123 showed similar enzymatic activity to Mn-SOD. To gain insights into the role of SODm-123 in oxidative stress tolerance, a series of experiments were conducted to assess the physiological and molecular responses of tomato plants when treated with SODm-123. The results showed that the levels of O2-• and H2O2 in tomato cells were affected by SODm-123 treatment, indicating that SODm-123 can control oxidative stress like Mn-SOD. The results also exhibited that SODm-123 increased the contents of photosynthetic pigments. However, it was noted that SODm-123 resulted in a reduction in the content of soluble sugar and MDA. These results indicate that SODm-123 promoted the efficiency of photosynthesis by regulating the content of H2O2. To further investigate the role of SODm-123 in controlling oxidative stress, a transcriptome analysis was used to identify differentially expressed genes (DEGs) associated with SODm-123 treatment. The results indicated that SODm-123 treatment resulted in 341 differentially expressed genes (DEGs) in treated tomato leaves at 96 h after treatment. Kyoto encyclopedia of genes and genomes (KEGG) revealed that DEGs were involved in pathways such as photosynthetic pigment biosynthesis, ABC transporters, sugar metabolism, and MAPK signaling, which further confirmed a positive role of SODm-123 in improving stress tolerance in plants. Overall, the results of this study suggest that SODm-123 promotes the growth and development of tomato seedlings and therefore can be used as a potential growth-promoting agent for plants.

Decomposition of hexamethyldisilane on a hot tungsten filament and gas-phase reactions in a hot-wire chemical vapor deposition reactor.

To study the effect of an Si-Si bond on gas-phase reaction chemistry in the hot-wire chemical vapor deposition (HWCVD) process with a single source alkylsilane molecule, soft ionization with a vacuum ultraviolet wavelength of 118 nm was used with time-of-flight mass spectrometry to examine the products from the primary decomposition of hexamethyldisilane (HMDS) on a heated tungsten (W) filament and from secondary gas-phase reactions in a HWCVD reactor. It is found that both Si-Si and Si-C bonds break when HMDS decomposes on the W filament. The dominance of the breakage of Si-Si over Si-C bond has been demonstrated. In the reactor, the abstraction of methyl and H atom, respectively, from the abundant HMDS molecules by the dominant primary trimethylsilyl radicals produces tetramethylsilane (TMS) and trimethylsilane (TriMS). Along with TMS and TriMS, various other alkyl-substituted silanes (m/z = 160, 204, 262) and silyl-substituted alkanes (m/z = 218, 276, 290) are also formed from radical combination reactions. With HMDS, an increasing number of Si-Si bonds are found in the gas-phase reaction products aside from the Si-C bond which has been shown to be the major bond connection in the products when TMS is used in the same reactor. Three methyl-substituted 1,3-disilacyclobutane species (m/z = 116, 130, 144) are present in the reactor with HMDS, suggesting a more active involvement from the reactive silene intermediates.