Intermolecular Charge-Transfer-Induced Strong Optical Emission from Herringbone H-Aggregates.

Luminescence in molecular aggregates can be quenched either by intermolecular charge transfer or by forming a dipole-forbidden lower Frenkel exciton in H-aggregate. Taking intermolecular charge transfer and excitonic coupling into a three-state model through localized diabatization, we demonstrate that the low-lying intermolecular charge-transfer state could couple with the upper bright Frenkel exciton to form dipole-allowed S1 that lies below the dark state, which accounts for the recent experimentally discovered strong luminescence in organic light-emitting transistors (OLETs) system with DPA and dNaAnt herringbone aggregates. The condition of forming such bright state is that the electron and hole transfer integrals, te and th, are of the same sign, and should be notably larger than the excitonic coupling (J), that is , te × th > 2J2. This theoretical finding not only rationalizes recent experiments but unravels an exciting scenario where strong luminescence and high charge mobilities become compatible, which is a preferable condition for both OLETs and electrically pumped lasing.

Temperature and solvent exposure response of three fatty acid peroxygenase enzymes for application in industrial enzyme processes.

Free fatty acids (FFAs) are a useful feedstock for a range of industrial chemical synthesis applications. However, efficiently converting FFAs to molecules for biofuel and other high-value chemicals requires more efficient and cost-effective catalysts. Cytochrome P450 fatty acid peroxygenases (CYP152) have a unique chemistry that allows use of the peroxide shunt pathway for biochemical conversion of FFAs. Known CYP152s are heat labile, however, requiring characterization of more thermotolerant versions for use in industrial applications. A fatty acid peroxygenase from Bacillus methanolicus (CYP152K6) was shown here to have a higher optimal reaction temperature than OleT (CYP152L1). CYP152K6 was stable up to 50 °C and showed great stability in 3% acetone and dimethylformamide. Stability in solvents helps the enzyme's substrates remain soluble in solution for more efficient catalysis, and heat stability allows enzymes to remain active longer during industrial processes.

Using Small Molecules to Enhance P450 OleT Enzyme Activity in Situ.

Cytochrome P450 OleT is a fatty acid decarboxylase that catalyzes the production of olefins with biofuel and synthetic applications. However, the relatively sluggish catalytic efficiency of the enzyme limits its applications. Here, we report the application of a novel class of benzene containing small molecules to improve the OleT activity. The UV-Vis spectroscopy study and molecular docking results confirmed the high proximity of the small molecules to the heme group of OleT. Up to 6-fold increase of product yield has been achieved in the small molecule-modulated enzymatic reactions. Our work thus sheds the light to the application of small molecules to increase the OleT catalytic efficiency, which could be potentially used for future olefin productions.

High Mobility Organic Lasing Semiconductor with Crystallization-Enhanced Emission for Light-Emitting Transistors.

The development of high mobility organic laser semiconductors with strong emission is of great scientific and technical importance, but challenging. Herein, we present a high mobility organic laser semiconductor, 2,7-diphenyl-9H-fluorene (LD-1) showing unique crystallization-enhanced emission guided by elaborately modulating its crystal growth process. The obtained one-dimensional nanowires of LD-1 show outstanding integrated properties including: high absolute photoluminescence quantum yield (PLQY) approaching 80 %, high charge carrier mobility of 0.08 cm2 V-1 s-1 , Fabry-Perot lasing characters with a low threshold of 86 µJ cm-2 and a high-quality factor of ≈2400. Furthermore, electrically induced emission was obtained from an individual LD-1 crystal nanowire-based light-emitting transistor due to the recombination of holes and electrons simultaneously injected into the nanowire, which provides a good platform for the study of electrically pumped organic lasers and other related ultrasmall integrated electrical-driven photonic devices.

Oxidative Decarboxylation of Short-Chain Fatty Acids to 1-Alkenes.

The enzymatic oxidative decarboxylation of linear short-chain fatty acids (C4:0-C9:0) employing the P450 monooxygenase OleT, O2 as the oxidant, and NAD(P)H as the electron donor gave the corresponding terminal C3 to C8  alkenes with product titers of up to 0.93 g L(-1) and TTNs of >2000. Key to this process was the construction of an efficient electron-transfer chain employing putidaredoxin CamAB in combination with NAD(P)H recycling at the expense of glucose, formate, or phosphite. This system allows for the biocatalytic production of industrially important 1-alkenes, such as propene and 1-octene, from renewable resources for the first time.

Covalent Bond Torsion-Enabled Unique Crystal-Phase Transformation of an Organic Semiconductor for Multicolor Light-Emitting Transistors.

High-mobility and color-tunable highly emissive organic semiconductors (OSCs) are highly promising for various optoelectronic device applications and novel structure-property relationship investigations. However, such OSCs have never been reported because of the great trade-off between mobility, emission color, and emission efficiency. Here, we report a novel strategy of molecular conformation-induced unique crystalline polymorphism to realize the high mobility and color-tunable high emission in a novel OSC, 2,7-di(anthracen-2-yl) naphthalene (2,7-DAN). Interestingly, 2,7-DAN has unique crystalline polymorphism, which has an almost identical packing motif but slightly different molecular conformation enabled by the small bond rotation angle variation between anthracene and naphthalene units. More remarkably, the subtle covalent bond rotation angle change leads to a big change in color emission (from blue to green) but does not significantly modify the mobility and emission efficiency. The carrier mobility of 2,7-DAN crystals can reach up to a reliable 17 cm2 V-1 s-1, which is rare for the reported high-mobility OSCs. Based on the unique phenomenon, high-performance light-emitting transistors with blue to green emission are simultaneously demonstrated in an OSC crystal. These results open a new way for designing emerging multifunctional organic semiconductors toward next-generation advanced molecular (atomic)-scale optoelectronics devices.

Improving the Performance of Red Organic Light-Emitting Transistors by Utilizing a High-k Organic/Inorganic Bilayer Dielectric.

Integration of electrical switching and light emission in a single unit makes organic light-emitting transistors (OLETs) highly promising multifunctional devices for next-generation active-matrix flat-panel displays and related applications. Here, high-performance red OLETs are fabricated in a multilayer configuration that incorporates a zirconia (ZrOx)/cross-linked poly(vinyl alcohol) (C-PVA) bilayer as a dielectric. The developed organic/inorganic bilayer dielectric renders high dielectric constant as well as improved dielectric/semiconductor interface quality, contributing to enhanced carrier mobility and high current density. In addition, an efficient red phosphorescent organic emitter doped in a bihost system is employed as the emitting layer for an effective exciton formation and light generation. Consequently, our optimized red OLETs displayed a high brightness of 16 470 cd m-2 and a peak external quantum efficiency of 11.9% under a low gate and source-drain voltage of -24 V. To further boost the device performance, an electron-blocking layer is introduced for ameliorated charge-carrier balance and hence suppressed exciton-charge quenching, which resulted in an improved maximum brightness of 20 030 cd m-2. We anticipate that the new device optimization approaches proposed in this work would spur further development of efficient OLETs with high brightness and curtailed efficiency roll-off.

Cellulosic hydrocarbons production by engineering dual synthesis pathways in Corynebacterium glutamicum.

BACKGROUND: Lignocellulose provides the only practical carbohydrates feedstock for sustainable bioproduction of hydrocarbons as future alternative of fossil fuels. Production of hydrocarbons from lignocellulose is achieved by a biorefinery process chain including pretreatment to breakdown the crystalline structure for cellulase-catalyzed hydrolysis, detoxification of inhibitory compounds generated during pretreatment, enzymatic hydrolysis to fermentable monosaccharide sugars, and fermentation to hydrocarbon products. The major barriers on fermentative production of hydrocarbons from lignocellulose include two aspects: one is the inherent stress of pretreatment-derived inhibitors on microbial cells, the other is the toxicity of hydrocarbons to cell membranes. The microbial cell factory should be tolerant to both inhibitor stress and hydrocarbons toxicity. RESULTS: Corynebacterium glutamicum was selected as the starting strain of hydrocarbons synthesis since it is well adapted to lignocellulose hydrolysate environment. The dual hydrocarbon synthesis pathways were constructed in an industrial C. glutamicum S9114 strain. The first pathway was the regular one in microalgae composed of fatty acyl-acyl carrier protein (fatty acyl-ACP) reductase (AAR) and aldehyde deformylating oxygenase (ADO) with fatty acyl-ACP as precursor. The second pathway was the direct decarboxylation of free fatty acid by fatty acid decarboxylase (OleT) using the rich fatty acids from the disruption of the transcriptional regulator fasR gene. The transmembrane transportation of hydrocarbon products was avoided by secretively expressing the fatty acid decarboxylase (OleT) to the extracellular space. The hydrocarbons generation from glucose reached 29.2 mg/L, in which the direct decarboxylation pathway contributed more than 70% of the total hydrocarbons generation, and the AAR-ADO pathway contributed the rest 30%. CONCLUSION: The dual hydrocarbon synthesis pathways (OleT and AAR-ADO pathways) were constructed in the inhibitors tolerant C. glutamicum S9114 strain for hydrocarbon production using lignocellulose feedstock as the starting feedstock. When corn stover was used for hydrocarbons production after dry acid pretreatment and biodetoxification, the hydrocarbons generation reached 16.0 mg/L. This study provided a new strategy for hydrocarbons synthesis using microbial cell factory suitable for lignocellulose feedstock.

Spectroscopic studies of the interaction between phosphorus heterocycles and cytochrome P450.

P450 fatty acid decarboxylase OleT from Staphylococcus aureus (OleTSA) is a novel cytochrome P450 enzyme that catalyzes the oxidative decarboxylation of fatty acids to yield primarily terminal alkenes and CO2 or minor α- and ß-hydroxylated fatty acids as side-products. In this work, the interactions between a series of cycloalkyl phosphorus heterocycles (CPHs) and OleTSA were investigated in detail by fluorescence titration experiment, ultraviolet-visible (UV-vis) and 31P NMR spectroscopies. Fluorescence titration experiment results clearly showed that a dynamic quenching occurred when CPH-6, a representative CPHs, interacted with OleTSA with a binding constant value of 15.2 × 104 M-1 at 293 K. The thermodynamic parameters (ΔH, ΔS and ΔG) showed that the hydrogen bond and van der Waals force played major roles in the interaction between OleTSA and CPHs. The UV-vis and 31P NMR studies indicated the penetration of CPH-6 into the interior environment of OleTSA, which greatly affects the enzymatic activity of OleTSA. Therefore, our study revealed an effective way to use phosphorus heterocyclic compounds to modulate the activity of cytochrome P450 enzymes.

Engineering Dielectric Materials for High-Performance Organic Light Emitting Transistors (OLETs).

Organic light emitting transistors (OLETs) represent a relatively new technology platform in the field of optoelectronics. An OLET is a device with a two-fold functionality since it behaves as a thin-film transistor and at the same time can generate light under appropriate bias conditions. This Review focuses mainly on one of the building blocks of such device, namely the gate dielectrics, and how it is possible to engineer it to improve device properties and performances. While many findings on gate dielectrics can be easily applied to organic light emitting transistors, we here concentrate on how this layer can be exploited and engineered as an active tool for light manipulation in this novel class of optoelectronic devices.

High-k Fluoropolymers Dielectrics for Low-Bias Ambipolar Organic Light Emitting Transistors (OLETs).

Organic light emitting transistors (OLETs) combine, in the same device, the function of an electrical switch with the capability of generating light under appropriate bias conditions. In this work, we demonstrate how engineering the dielectric layer based on high-k polyvinylidene fluoride (PVDF)-based polymers can lead to a drastic reduction of device driving voltages and the improvement of its optoelectronic properties. We first investigated the morphology and the dielectric response of these polymer dielectrics in terms of polymer (P(VDF-TrFE) and P(VDF-TrFE-CFE)) and solvent content (cyclopentanone, methylethylketone). Implementing these high-k PVDF-based dielectrics enabled low-bias ambipolar organic light emitting transistors, with reduced threshold voltages (<20 V) and enhanced light output (compared to conventional polymer reference), along with an overall improvement of the device efficiency. Further, we preliminary transferred these fluorinated high-k dielectric films onto a plastic substrate to enable flexible light emitting transistors. These findings hold potential for broader exploitation of the OLET platform, where the device can now be driven by commercially available electronics, thus enabling flexible low-bias organic electronic devices.

Enhanced P450 fatty acid decarboxylase catalysis by glucose oxidase coupling and co-assembly for biofuel generation.

Cytochrome P450 OleT is a fatty acid decarboxylase that uses hydrogen peroxide (H2O2) to catalyze the production of terminal alkenes, which are industrially important chemicals with biofuel and synthetic applications. Despite its requirement for large turnover levels, high concentrations of H2O2 may cause heme group degradation, diminishing enzymatic activity and limiting broad application for synthesis. Here, we report an artificial enzyme cascade composed of glucose oxidase (GOx) and OleTSA from Staphylococcus aureus for efficient terminal alkene production. By adjusting the ratio of GOx to OleTSA, the GOx-based tandem catalysis shows significantly improved product yield compared to the H2O2 injection method. Moreover, the co-assembly of the GOx/OleTSA enzymes with a polymer, forming polymer-dual enzymes nanoparticles, displays improved activity compared to the free enzyme. This dual strategy provides a simple and efficient system to transform a naturally abundant feedstock to industrially important chemicals.

Electrical behaviour of MEH-PPV based diode and transistor.

The potential of organic semiconductor based devices for light generation is demonstrated by the commercialisation of display technologies using organic light emitting diode (OLED). In OLED, organic materials plays an important role of emitting light once the current is passed through. However OLED have drawbacks whereby it suffers from photon loss and exciton quenching. Organic light emitting transistor (OLET) emerged as a new technology to compensate the efficiency and brightness loss encountered in OLED. The structure has combinational capability to switch the electronic signal such as the field effect transistor (FET) as well as to generate light. Different colours of light could be generated by using different types of organic material. The light emission could also be tuned and scanned in OLET. The studies carried out in this paper focuses on investigation of fabricated MEH-PPV based OLED and also OLET via current voltage characteristics. These studies will continue with a view to develop an optimised MEH-PPV based OLET.