Arylene bisimides with triarylamine N-substituents as new solution processable organic semiconductors: Synthesis,spectroscopic, electrochemical and electronic properties

New solution processable organic semiconductors, consisting of pyrromelitic, naphthalene or perylene bisimide core and triarylamine N-substituents, have been synthesized. All three compounds are electrochemically active and undergo quasi-reversible oxidation and reduction as evidenced by cyclic voltammetry investigations. The oxidation process involves the transformation of the triarylamine substituents into radical cations as proven spectroscopically and spectroelectrochemically. The reduction process occurs at the arylene bisimide core leading to the formation of a radical anion and eventually a dianion in the second step. These findings are in perfect agreement with the DFT calculations which show that in the synthesized molecules the HOMO orbital is located on the triarylamine moiety whereas the LUMO one on the bisimide core. In all molecules studied the electrochemically determined ionization potential (IP) is slightly higher than 5.0 eV whereas in naphthalene and perylene derivatives the electron affinity (EA) is close to ?3.9 eV. These values fulfill the requirements for n-type (electron) semiconductors in air operating n-channel field effect transistors (FETs) as well as for p-type (hole) conductors in p-channel FETs. To verify whether the newly synthesized compounds exhibit the expected electrical transport properties all organic (CYTOP dielectric) test transistors were fabricated. All three semiconductors showed no field effect in the n-channel configuration. To the contrary, they could be used in p-channel FETs showing, in the saturation regime, the hole mobility approaching 10^?4 cm² V^?1 s^?1 – the value which slightly exceeds that measured for low molecular weight, amorphous triarylamine semiconductors.     

Trajectory Analysis of Forest Cover Change in the Tropical Dry Forest of Burkina Faso,West Africa

Forest cover decline is one of the most important environmental issues in the tropics. The present study was carried out in Burkina Faso, West Africa, and aimed at assessing the trajectories of forest cover change and measuring landscape metrics of the trajectory classes in order to better understand the processes of change. Landsat and ASTER images acquired over a period of 30 years were used for cover change detection and the Fragstats package was used to compute landscape metrics with five unifying change classes. Results showed a substantial increase in cropland with concurrent decline in forest cover. Deforestation represented 63% of the Percentage of Landscape (PLAND) in 2006, while reforestation accounted for only 28%. Both of these classes had high Normalized Landscape Shape Index (NLSI) values, indicating that they were present as scattered small patches. The old cultivation (30-year permanent cropland) was aggregated (IJI ≈ 0) while deforestation exhibited highly interspersed patches. The old forest and old cultivation presented lower Area Weighted Fractal Dimension Index (FRAC_AM), but deforestation and reforestation had the higher FRAC_AM. These results confirmed that there was a high level of deforestation and fragmentation in southern Burkina Faso and justify the need for a proper management plan to ensure the sustainable use of forest resources.     

Temperature stability of a pure metakaolin based K-geopolymer: Part 2. Variations in the mesoporous network and its rehydration stability

The thermal behavior of a model MK-based K-geopolymer was investigated between room temperature and 1400°C in order to evaluate its potentiality for high-temperature applications. The purpose of our study was to monitor the behavior of a geopolymer during a temperature rise in order to better understand its variations with respect to temperature. The works from the present paper focus only changes in the porous network; it follows a first part devoted to variations in the mineral matrix. The results obtained here show that the geopolymer material preserves its porous integrity up to 800°C, while maintaining the reversibility of water exchanges corresponding to about 25 weight percent. Together with the results of part 1, the findings of this study allow us to affirm that geopolymer materials are only very little affected by temperatures up to 800°C, or even 900°C (keeping its mesoporous amorphous structure).     

Microtribology,squeeze, and friction of the colloidal layer

Lubricant films containing colloidal overbased calcium salts have particular effects on detergency and on the wear process. The mechanical properties of such boundary films are very dependent on the process conditions, and are essentially a result of physico-chemical transformations of the colloid. Three types of films were compared: a film obtained by the drying of the base solvent, a film due to the compaction of the colloid between two steel surfaces, and a friction film obtained with this type of lubricant. Adsorption, compaction, and shear transformations induce a solid film. The pressure effect on the frictional behaviour of these colloidal films has been investigated using a surface force apparatus for low contact pressure (10⁴ to 10⁶ Pa), and using tribometers supporting heavy loads for the analysis of the high pressure domain. Above a critical pressure, evaluated at 10⁶ Pa, the colloidal film does not flow, but forms a compacted mattress sliding on the surface plane and squeezing a molecular layer of lubricant.     

Clenbuterol residue analysis by HPLC-HPTLC in urine and animal tissues

A method for clenbuterol residue analysis in urine and animal tissues has been developed. The detection limits are 0.25 micrograms/l and 0.5 micrograms/kg, respectively. The recovery in urine varies from 85% to 90% and in animal tissues from 70% to 74%. The beta 2-agonist was liberated from the tissues by an enzymatic digestion, purified on Chem Elut columns using alkaline conditions and extracted with 0.01 mol/l HCl. Clenbuterol was quantified by high-performance liquid chromatography (HPLC) on a RP-8 column and a post-column reaction procedure. High-performance thin-layer chromatography (HPTLC) was performed on silica gel 60 plates and clenbuterol visualized by means of the modified Ehrlich's TLC spray reagent. Since this method is sensitive, as is HPLC, it was used to obtain a confirmation and to exclude false positive results.     

Cover Feature: A Comparative Study of in vitro Assays for Predicting the Nonspecific Binding of PET Imaging Agents in vivo (ChemMedChem 7/2020)

Nonspecific binding (NSB) is a key parameter in optimizing PET imaging tracers. We compared the ability to predict NSB of three available methods: LIMBA, rat f_u,brain, and CHI(IAM). Even though NSB is often associated with lipophilicity, we observed that logD does not correlate with any of these assays, clearly indicating that lipophilicity, while influencing NSB, is insufficient to predict it. A cross-comparison of the methods showed that all three correlate and are useful predictors of NSB. The three assays, however, rank the molecules slightly differently, illustrating the challenge of comparing molecules within a narrow chemical space. We also noted that CHI(IAM) values more effectively predict V_NS, a measure of in vivo NSB in the human brain. CHI(IAM) measurements might be a closer model of the actual physicochemical interaction between PET tracer candidates and cell membranes, and seems to be the method of choice for the optimization of in vivo NSB.     

Modified Galacto- or Fuco-Clusters Exploiting the Siderophore Pathway to Inhibit the LecA- or LecB-Associated Virulence of Pseudomonas aeruginosa

Galacto- and fuco-clusters conjugated with one to three catechol or hydroxamate motifs were synthesised to target LecA and LecB lectins of Pseudomonas aeruginosa (PA) localised in the outer membrane and inside the bacterium. The resulting glycocluster–pseudosiderophore conjugates were evaluated as Trojan horses to cross the outer membrane of PA by iron transport. The data suggest that glycoclusters with catechol moieties are able to hijack the iron transport, whereas those with hydroxamates showed strong nonspecific interactions. Mono- and tricatechol galactoclusters ( G1C and G3C ) were evaluated as inhibitors of infection by PA in comparison with the free galactocluster ( G0 ). All of them exhibited an inhibitory effect between 46 to 75 % at 100 μM, with a higher potency than G0 . This result shows that LecA localised in the outer membrane of PA is involved in the infection mechanism.     

Cation Effect on the Binary and Ternary Phase Behaviors of Double-Tailed Methanesulfonate Amphiphiles

A series of symmetrical dialkyl methanesulfonate amphiphiles [DiC _n CHSO ₃ ] _m M (n = 6, 7, 8) with different counter cations (M^m+ = H⁺, Li⁺, Na⁺, K⁺, Cu²⁺, Zn²⁺, Mg²⁺, Ca²⁺, Sc³⁺) were synthesized in five steps. Their solubility and critical micelle concentration (CMC) in water were determined highlighting a huge effect of the chain length and the nature of the cation. The hydrophilic–lipophilic balance of the surfactants were assessed with the phase inversion temperature (PIT)-slope method based on the deviation from the PIT of the reference C₁₀E₄/n-octane/0.01 M NaCl_(aq) emulsion through addition of increasing amounts of the dialkyl methanesulfonates. The hydrophilicity of the surfactants was thus ranked in terms of dPIT/dx_sulfonate. A “cation” scan with the [DiC ₆ CHSO ₃ ] _m M /benzene/water systems at f_w = 0.5 was finally performed confirming the hydrophilicity ranking obtained with the PIT-slope method. It revealed that the [DiC ₆ CHSO ₃ ] ₂ Mg behaves as a “Balanced Surfactant” able to form spontaneously a three-phase microemulsion system (Winsor III) just in the presence of water and oil, in the same way as the catalytic surfactant dimethyldioctylammonium molybdate, which has the same PIT-slope.     

Single crystals morphology of biodegradable double crystalline PLLA-b-PCL diblock copolymers

The morphology of solution grown single crystals of a series of double crystalline diblock copolymers derived from l-lactide and ?-caprolactone has been investigated by means of transmission electron microscopy. The copolymers had a variable composition with a poly(l-lactide) weight percentage that ranged between 81 and 10%. All samples had a low polydispersity index (1.4-1.1) and a similar number average molecular weight (20,000-35,000 g/mol).Bulk crystallization and melting behaviour of diblock copolymers were evaluated by DSC and the results demonstrated the double crystalline nature of the samples. Fractionated crystallization clearly occurred in copolymers having an intermediate composition.Isothermal crystallizations were performed in dilute n-hexanol solutions at temperatures that ranged between 80 and 50 °C. Crystal morphologies were dependent on the crystallization temperature and even on the composition. Thus, the inability of poly(?-caprolactone) (PCL) blocks to crystallize between 80 and 70 °C rendered lozenge, truncated and spindle-shaped crystals associated to the poly(l-lactide) (PLLA) block. These usually had thicker edges due to PLLA overgrowths that mainly took place in their periphery. However, an overgrowth of irregular PCL crystals during subsequent cooling and crystallization at room temperature was also detected. Complex morphologies constituted by lamellar crystals of both PCL and PLLA blocks were developed at intermediate temperatures (70-65 °C), whereas elongated hexagonal morphologies mainly associated to the PCL block were detected at the lowest crystallization temperature. In general, electron diffraction patterns showed for all samples’ reflections associated to both poly(?-caprolactone) and poly(l-lactide) (α-form) crystals. The relative intensity between the two types of reflections varied according to the copolymer composition.     

Extraction and Analysis of the Essential Oil of the Needles and Twigs of White Spruce Picea Glauca (Moench) Voss

Abstract

The constituents of the essential oil extracted from the needles and twigs of white spruce - Picea glauca (Moench) Voss -by steam distillation are analyzed by GC-MS and GC with authentic samples. The analysis allows for the Identification of 39 constituents.