Effect of additive length and chemistry on the morphology of blends of conjugated thiophenes and fullerene derivative acceptor molecules

Small molecule additives have been shown to increase the device efficiency of conjugated polymer (donor) and fullerene derivative (acceptor) based organic solar cells by modifying the morphology of the device active layer. In this paper we conduct a systematic study of how additives affect the donor‐acceptor morphology using molecular dynamics simulations of blends of thiophene‐based oligomers, mimicking poly(3‐dodecylthiophene) (P3DDT) or poly(2,2′:5′,2”‐3,3”‐didocyl‐terthiophene) (PTTT), and fullerene derivatives with additives of varying length and chemical functionalization, mimicking experimentally used additives like methyl ester additives, diiodooctane, and alkanedithiols. We find that functionalization of additives with end groups that are attracted to acceptor molecules are necessary to induce increased donor‐acceptor macrophase separation. In blends where acceptors intercalate between oligomer alkyl side chains, functionalized additives decrease acceptor intercalation. Functionalized additives with shorter alkyl segments increase acceptor macrophase separation more than additives with same chemical functionalization but longer alkyl segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1046–1057     

Cyclic voltammetric studies of certain industrially potential iron chelate catalysts

 For the analysis of infrared spectroscopic bands and complex patterns partial cross correlation functions of a sample spectrum with reference spectra are calculated. The chosen ranges of the spectra are based on empirical knowledge of infrared spectrum structure correlations. The normalised maxima of the partial cross correlation functions are interpreted as fuzzy truth values and are combined by fuzzy logical operators. By application of that procedure larger common substructures will be derived from the reference spectra than by a maximum common substructure search based on the complete spectra. Received: 30 October 1996/Revised: 24 February 1997/Accepted: 26 February 1997     

Pseudopotential in the study of superconducting state parameters of metallic glasses

A well recognized model potential is used to study the superconducting state parameters (SSP) viz. electron–phonon coupling strength λ, Coulomb pseudopotential μ¹, transition temperature T_C, isotope effect exponent α and effective interaction strength N₀V of some binary metallic glasses of simple, non-simple and transition metals. Five local field correction functions proposed by Hartree (H), Taylor (T), Ichimaru–Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) are used in the present investigation to study the screening influence on the aforesaid properties. Instead of using Vegard’s law, pseudo-alloy-atom model (PAA) in the present investigation is proposed and found successful. The present results of the SSP are found in qualitative agreement with other such earlier reported data wherever exist, which confirms the superconducting phase in the metallic glasses.     

Γ andX bandgap hydrostatic deformation potentials for epitaxial In0.52Al0.48As on InP(001)

The pressure dependence of the direct and indirect bandgap of epitaxial In_0.52Al_0.48As on InP(001) substrate has been measured using photoluminescence up to 92 kbar hydrostatic pressure. The bandgap changes from Γ toX at an applied pressure of ∼ 43 kbar. Hydrostatic deformation potentials for both the Γ andX bandgaps are deduced, after correcting for the elastic constant (bulk modulus) mismatch between the epilayer and the substrate. For the epilayer we obtain and+(2.81±0.15)eV for the Γ andX bandgaps respectively. From the pressure dependence of the normalized Γ-bandgap photoluminescence intensity a Γ-X lifetime ratio, (τ_Γ/τ _X ), of 4.1×10⁻³ is deduced.     

Synthesis and characterization of 3-phenylethynyl endcapped matrix resins

The synthesis of 3-phenylethynylphenol, and its applicability as a high temperature cross-linking endcap for high T_g polyarylene ethers is described. It was synthesized in high yields and purity using the palladium catalyzed coupling reaction between the protected 3-bromo or iodo phenol and phenylacetylene. The yield of the reaction was found to be highly dependent on the structure of the halide used, the reaction temperature, and the concentration of phenylacetylene. The use of the protected phenol in the palladium catalyzed reaction was also extended to the high yield synthesis of 3-ethynylphenol and protected 4-ethynylphenols. The complete synthesis of 3-phenylethynylphenol, 3-ethynylphenol, and protected 4-ethynylphenol in high yields has been demonstrated and is discussed herein. Three new phenylethynyl functionalized arylene ether matrix resins have been synthesized in high yields and purity by reacting 3-phenylethynylphenol with 4,4′-dichlorodiphenyl sulfone, 4,4′-difluorobenzophenone, and bis(4-fluorophenyl)phenyl phosphine oxide, via nucleophilic poly(arylene ether) synthesis conditions. These low molecular weight materials undergo thermally induced chain extension/branching to yield an insoluble three-dimensional network at reaction temperatures of around 380°C. The low molecular weight arylene ethers endcapped with the phenylethynyl group demonstrate excellent flow characteristics and a wide processing window of about 250°C. Crosslinking of the 4,4′-bis(3-phenylethynyl phenoxy)diphenyl sulfone system for 30 min at 350°C in air afforded a T_g value of 265°C by differential scanning calorimetry measurements. Trace metal analysis for palladium and copper showed absence of these metals that would otherwise detract from the excellent thermal stability. The synthesis and characterization of these phenylethynyl endcapped arylene ether matrix resins is discussed. © 1995 John Wiley & Sons, Inc.     

Polymer-coated hollow-fiber microextraction of estrogens in water samples with analysis by gas chromatography-mass spectrometry

A novel sorbent, dihydroxylated polymethylmethacrylate (DHPMM), coated on hollow-fiber membrane, is used for the polymer-coated hollow-fiber microextraction of trace amounts of natural and synthetic estrogens, such as diethylstilbestrol, estrone, 17beta-estradiol and 17alpha-ethynylestradiol, in aqueous samples. In this procedure, estrogens were extracted using the functionalized polar DHPMM polymer with derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide followed by gas chromatography-mass spectrometric analysis. The detection limits for estrogens in aqueous sample were between 0.03 and 0.8 ng l(-1) and the calibration curves were linear over the concentration range 0.05-10 microgl(-1) and had correlation coefficients of >0.994. The relative standard deviations (RSDs) were <15% (n = 3). This simple, accurate, sensitive and selective analytical method is applicable to the determination of trace amounts of estrogens in reservoir and potable water samples.     

Studies on ion association. Calorimetric study of the formation of monoazido complexes of Ni(II), Zn(II) and Cd(II)

From rehydration experiments the hydrates Ba(OH)₂ · 8 H₂O, Ba(OH)₂ · 3 H₂O β-Ba(OH)₂, · 1 H₂O, and γ-Ba(OH)₂ · 1 H₂O have been found in the system Ba(OH)₂-H₂O. Thermoanalytical measurements (DTA, TG, DTG, high temperature X-ray diffraction, high temperature Raman scattering) on these hydrates are reported. Thermal decomposition of Ba(OH)₂ · 8 H₂O and Ba(OH)₂ · 3 H₂O always results in the formation of β-Ba(OH)₂ · 1 H₂O, the stable form of the monohydrates at ambient temperature. Dehydration of β- and γ-Ba(OH)₂ · 1 H₂O, both of which form anhydrous β-Ba(OH)₂ as the first product of decomposition, starts at 105 and 115°C, respectively. Single crystals of Ba(OH)₂ · 3 H₂O and γ-Ba(OH)₂ · 1 H₂O were prepared from Ba(OH)₂ · 8 H₂O meltings and from ethanolic solutions of Ba(OH)₂ , respectively. The crystal data are: Ba(OH)₂ · 3 H₂O (orthorhombic, Pnma): a = 764.0(2), b = 1140,3(5), c = 596.5(1) pm, Z = 4; γ-Ba(OH)₂ · 1 H₂O (monoclinic, P2₁/m or P2₁): a = 704.9(2), b = 418.4(1), c = 633.3(1) pm, β = 111.45(2)°, Z = 2.     

Synthesis and Langmuir studies of bivalent and monovalent alpha-D-mannopyranosides with lectin Con A

Highly avid interaction between carbohydrate ligands and lectin receptors nominally requires the ligand presentation in a clustered form. We present herein an approach involving Langmuir monolayer formation of the sugar ligands and the assessment of their lectin binding at the air-water interface. Bivalent alpha-D-mannopyranoside containing the glycolipid ligand was used to study its binding profiles with lectin Con A, in comparison to the corresponding monovalent glycolipid. In addition to the bivalent and monovalent nature of the glycolipid ligands at the molecular level, the ligand densities at the monolayer level were varied with the aid of a nonsugar lipid molecule so as to obtain mixed monolayers with various sugar-nonsugar ratios. Lectin binding of bivalent and monovalent ligands at different ratios was monitored by differential changes in the surface area per molecule of the mixed monolayer, with and without the lectin. The present study shows that maximal binding of the lectin to the bivalent ligand occurs at lower sugar densities at the interface ( approximately 10% sugar in the mixed monolayer) than for that of the monovalent ligand ( approximately 20% sugar in the mixed monolayer). It is observed that complete coverage of the monolayer with only the sugar ligands does not allow all of the sugars to be functionally active.     

Potentiometric estimation of sulfide ion using the Fe(III)-EDTA complex

The Fe(III)-EDTA complex reacts with sulfide ion in a fast electron transfer reaction, oxidising the latter to elemental sulfur and getting itself reduced to Fe(II). The reaction has been developed for the quantitative estimation of sulfide ion by titration against the Fe(III)-EDTA complex, measuring the redox potential of the system. Repeated use of a given quantity of the complex solution by the process of regeneration has been demonstrated. The possibility of its practical application in liquid phase oxidation processes of recovering sulfur from H₂S is emphasized.