Development of Petri Net-Based Dynamic Model for Improved Production of Farnesyl Pyrophosphate by Integrating Mevalonate and Methylerythritol Phosphate Pathways in Yeast

In this case study, we designed a farnesyl pyrophosphate (FPP) biosynthetic network using hybrid functional Petri net with extension (HFPNe) which is derived from traditional Petri net theory and allows easy modeling with graphical approach of various types of entities in the networks together. Our main objective is to improve the production of FPP in yeast, which is further converted to amorphadiene (AD), a precursor of artemisinin (antimalarial drug). Natively, mevalonate (MEV) pathway is present in yeast. Methyl erythritol phosphate pathways (MEP) are present only in higher plant plastids and eubacteria, but not present in yeast. IPP and DAMP are common isomeric intermediate in these two pathways, which immediately yields FPP. By integrating these two pathways in yeast, we augmented the FPP synthesis approximately two folds higher (431.16 U/pt) than in MEV pathway alone (259.91 U/pt) by using HFPNe technique. Further enhanced FPP levels converted to AD by amorphadiene synthase gene yielding 436.5 U/pt of AD which approximately two folds higher compared to the AD (258.5 U/pt) synthesized by MEV pathway exclusively. Simulation and validation processes performed using these models are reliable with identified biological information and data.     

Exciton Diffusion in Polyfluorene Copolymer Thin Films: Kinetics,Energy Disorder and Thermally Assisted Hopping

A series of {(9,9‐dioctylfluorene)_0.7?x‐(dibenzothiophene‐S,S‐dioxide)_0.3‐[4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole]_x} (PFS₃₀‐TBTx), where x represents the minor percentage of the red emitter 4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole (TBT) randomly incorporated into the copolymer backbone, is investigated in order to follow the energy transfer from PFS₃₀ to TBT moieties. The emission of the donor poly[(9,9‐dioctylfluorene)_0.7‐(dibenzothiophene‐S,S‐dioxide)_0.3 identified by PFS₃₀ and peaking at 450 nm, is clearly quenched by the presence of the red TBT chromophore emitting at 612 nm, with an isoemissive point observed when the spectra are collected as a function of temperature. A plot of the ratio between the TBT and PFS₃₀ emissions as a function of the reciprocal of temperature gives a clear linear trend between 290 and 200 K, with an activation energy of 20 meV and showing a turn over to a non‐activated regime below 200 K. Picosecond time‐resolved fluorescence decays collected at the PFS₃₀ and TBT emission wavelengths, show a decay of the PFS₃₀ emission and a fast build‐in, followed by a decay, of the TBT emission, confirming that the population of the TBT excited state occurs during the PFS₃₀ lifetime(～600 ps). The population of the TBT excited state occurs on a time regime around 150 ps at 290 K, showing an energy barrier of 20 meV that turns over to a non‐activated regime below 200 K in clear agreement with the steady‐state data. The origin of the activation barrier is attributed to the presence of physical and energetic disorder, affected by fast thermal fluctuations that dynamically change the energy landscape and control the exciton migration through the polymer density of states.     

Synthesis and characterization of fluorene‐based oligomers and polymers incorporating N‐arylphenothiazine‐S,S‐dioxide units

A series of 3,7‐bis(9,9‐di‐n‐hexylfluoren‐2‐yl)‐N‐arylphenothiazine‐S,S‐dioxide trimers and (9,9‐di‐n‐octylfluorene‐2,7‐diyl‐co‐N‐arylphenothiazine‐S,S‐dioxide) co‐polymers, with varying ratios of phenothiazine‐S,S‐dioxide units, have been prepared in good yields by palladium‐catalyzed cross‐coupling reactions. The materials are deep blue emitters and show no solvatochromism or evidence for an intramolecular charge‐transfer state. The photoluminescence quantum yields of the trimers are ?_PL 15–30% in solution and 14–25% in films. The polymers demonstrated very high values in solution (?_PL 74–84%) and ?_PL values in films of 28–47%. The estimated HOMO energy levels are between ?5.64 and ?5.62 eV for the polymers with 15% incorporation of the phenothiazine‐S,S‐dioxide units. An analogous N‐arylphenothiazine co‐polymer shows significantly red shifted absorption and emission. Solution electrochemical data and density functional theory calculations are also presented. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

The β Phase Formation Limit in Two Poly(9,9‐di‐n‐octylfluorene) based Copolymers

Random copolymers of poly(9,9‐di‐n‐octylfluorene) (PF8) incorporating 0, 8, 12, 15, and 20% dibenzothiophene (DBT), and copolymers with 2, 5, 8, 12, and 15% dibenzothiophene‐S,S‐dioxide (S‐unit) were synthesised. Absorption and emission spectra of thin films indicate that the DBT system shows a linear decrease of toluene vapour induced β phase with increasing DBT content to a 20% cutoff, whilst in the S‐unit copolymers the β phase is present up to 12% co‐monomer content, and at 15% the characteristic absorption peak is absent or masked. These results demonstrate the limits, in thin films, at which the β phase can be formed in widely used PF8 copolymer systems for device applications and clearly show that it is practical to use copolymers having electron or hole transport units in the polyfluorene backbone and still be able to form efficient β phase emission sites.