Improved synthesis of N-alkyl substituted dithieno[3,2-b:2′,3′-d]pyrroles

A new, convergent and improved synthetic method to prepare N-alkyl substituted dithienopyrroles is described. The procedure consists of a Pd-catalyzed amination of 3,3′-dibromo-2,2′-bithiophene. The reaction conditions were optimized, which makes this method applicable to prepare these molecules easily in high yields and on a large scale.     

CFD modelling and wind tunnel validation of airflow through plant canopies using 3D canopy architecture

The efficiency of pesticide application to agricultural fields and the resulting environmental contamination highly depend on atmospheric airflow. A computational fluid dynamics (CFD) modelling of airflow within plant canopies using 3D canopy architecture was developed to understand the effect of the canopy to airflow. The model average air velocity was validated using experimental results in a wind tunnel with two artificial model trees of 24 cm height. Mean air velocities and their root mean square (RMS) values were measured on a vertical plane upstream and downstream sides of the trees in the tunnel using 2D hotwire anemometer after imposing a uniform air velocity of 10 m s^?1 at the inlet. 3D virtual canopy geometries of the artificial trees were modelled and introduced into a computational fluid domain whereby airflow through the trees was simulated using Reynolds-Averaged Navier–Stokes (RANS) equations and k-ε turbulence model. There was good agreement of the average longitudinal velocity, U between the measurements and the simulation results with relative errors less than 2% for upstream and 8% for downstream sides of the trees. The accuracy of the model prediction for turbulence kinetic energy k and turbulence intensity I was acceptable within the tree height when using a roughness length (y₀ = 0.02 mm) for the surface roughness of the tree branches and by applying a source model in a porous sub-domain created around the trees. The approach was applied for full scale orchard trees in the atmospheric boundary layer (ABL) and was compared with previous approaches and works. The simulation in the ABL was made using two groups of full scale orchard trees; short (h = 3 m) with wider branching and long (h = 4 m) with narrow branching. This comparison showed good qualitative agreements on the vertical profiles of U with small local differences as expected due to the spatial disparities in tree architecture. This work was able to show airflow within and above the canopy in 3D in more details.     

Regioregular Poly[3‐(4‐alkoxyphenyl)thiophene]s: Evidence for a Two‐Step Aggregation Process

Summary: A chiral, regioregular poly[3‐(4‐alkoxyphenyl)thiophene] has been prepared and studied. Films prepared by fast evaporation of the solvent, consist of random‐coils, while films prepared by slow evaporation are composed of chirally aggregated, coplanar strands. Heat treatment transforms the random‐coils into aggregated films via an intermediate state, which was characterized as chiral, coplanar, unaggregated polymer strands.

Overview of the possible aggregation processes.     

Synthesis and nonlinear optical properties of high glass transition poly(maleimide-4-phenylstyrene)s

Nonlinear optical polymers with high T_g were prepared by polymer analogous reaction of maleic anhydride copolymers with aminoalkyl-functionalized azo chromophores. Poled films of the polymers show a good nonlinear optical response that is stable at temperatures up to 125°C.     

Nonlinear optical properties of polymers and thin polymer films

An introduction to nonlinear optics (NLO) and the major challenges in the field of NLO-properties of polymeric materials, is given in this paper. Methods for the investigation of nonlinear optical properties of [4-(2-methacryloxyethyl)methylamino]-4′-cyanoazobenzene copolymers with methyl methacrylate (MMA) are demonstrated: Electric Field Induced Second Harmonic Generation (EFISHG), Hyper Rayleigh Scattering (HRS), Second Harmonic Generation (SHG) in floating monolayers and SHG in poled polymer films. An example of phase-transition analysis by SHG is given.     

Mass transfer characteristics for VOC permeation through flat sheet porous and composite membranes: The impact of the different membrane layers on the overall membrane resistance

In this paper, the mass transfer coefficients for trichloroethylene (TCE), toluene (TOL) and dimethyl sulfide (DMS) are experimentally determined for different porous and composite membranes. For polypropylene/polyvinylidenedifluoride porous layer/thin film polydimethylsiloxane dense layer composite membranes, membrane mass transfer coefficients are 2.55E−03, 2.82E−03 and 2.90E−03 m/s for TCE, TOL and DMS in N₂ at 30.0 ± 0.1 °C, respectively. For polyester/polyacrylonitrile porous layer/thin film polydimethylsiloxane dense layer composite membranes, they are higher, namely 4.28E−03, 4.55E−03 and 4.81E−03 m/s for TCE, TOL and DMS in N₂ at 30.0 ± 0.1 °C, respectively. Analysis of the contribution of the dense layer of both composite membranes to the total membrane resistance for mass transfer, showed that this contribution was small for both composite membranes. The higher mass transfer coefficients of the thin film polydimethylsiloxane composite membranes from this study in comparison to others from the literature are primarily due to improvement of the mass transfer characteristics of the porous layer. Analysis of the mass transfer characteristics of the different porous layers of which the total porous layer is composed, showed that the contribution of the porous “backing” layer for mechanical support can be substantial in comparison to the porous layer in contact with the dense layer.     

Design, synthesis, linear, and nonlinear optical properties of conjugated (porphinato)zinc(II)-based donor-acceptor chromophores featuring nitrothiophenyl and nitrooligothiophenyl electron-accepting moieties

An extensive series of conjugated (porphinato)zinc(II)-based chromophores featuring nitrothiophenyl and nitrooligothiophenyl electron-accepting moieties has been synthesized using metal-catalyzed cross-coupling reactions involving [5-bromo-15-triisopropylsilylethynyl-10,20-diarylporphinato]zinc(II) and an unusual electron-rich Suzuki-porphyrin synthon, [5-(4-dimethylaminophenylethynyl)-15-(4',4',5',5'-tetramethyl[1',3',2']dioxaborolan-2'-yl)-10,20-diarylporphinato]zinc(II), with appropriately functionalized aryl and thienyl precursors. These donor-acceptor chromophores feature thiophenyl, [2,2']bithiophenyl, and [2,2';5',2' ']terthiophenyl units terminated with a 5-nitro group; one series of structures features these acceptor moieties appended directly to the porphyrin macrocycle meso-carbon position, while a second set utilizes an intervening meso-ethynyl moiety to modify porphyrin-to-thiophene conjugation. The dynamic hyperpolarizability of these compounds was determined from hyper-Rayleigh light scattering (HRS) measurements carried out at fundamental incident irradiation wavelengths (lambda(inc)) of 800 and 1300 nm; interestingly, measured beta(1300) values ranged from 650 --> 4350 x 10(-30) esu. The combined linear and nonlinear optical properties of these compounds challenge the classical concept of the nonlinearity/transparency tradeoff in charge-transfer chromophores: the magnitude of the molecular hyperpolarizability is observed to vary substantially despite approximately uniform ground-state absorptive signatures for a given porphyrin-to-thiophene linkage topology. These data show that these neutral dipolar molecules can express substantial beta(1300) values; such conjugated, electronically asymmetric porphyrin-thiophene chromophores may thus find utility for electrooptic applications at telecom-relevant wavelengths.