Impact of environmentally friendly processing solvents on the properties of blade‐coated polymer solar cells

High‐performance polymer solar cells (PSCs) are typically fabricated by spin coating in inert atmosphere from toxic halogenated solvents such as 1,2‐dichlorobenzene (o‐DCB) and chlorobenzene. This fabrication process is potentially hazardous for both the humans and the environment and dramatically impacts the possibility for the organic photovoltaic technology to be adopted at large scale. In this work, efficient PSCs blade coated in air using nonhalogenated 1,2,4‐trimethylbenzene (TMB) as processing solvent are demonstrated. The active layer, based on a previously synthesized benchmark polymer PFQ2T‐benzodithiophene blended with [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM), showed an enhanced solid‐state aggregation induced by the use of TMB. Compared to o‐DCB‐processed devices, the solar cells fabricated from TMB resulted 10% more efficient with a power conversion efficiency of 4.20%. Interestingly, the improved photovoltaic performance resulted from the combination of synergic effects promoted by a more favorable film morphology, such as high exciton dissociation efficiency and lower bimolecular recombinations resulting in higher charge collection efficiency at the electrodes. The positive effect of TMB, compared to that of commonly employed halogenated solvents, confirms the great potential of this approach for the development of efficient PSCs for practical applications with reduced environmental impact. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 487–494     

Synthesis of alcohol ester 12 in 1, 8‐diazabicyclo [5.4.0] undec‐7‐ene (DBU)‐based Self‐separation catalytic system

The synthesis of alcohol ester 12 is one of the valuable industrial processes, but it was impeded by poor separating property and recycling ability of the catalytic systems. Herein, four novel DBU‐based basic ionic liquids (DBILs) of [BDBU]IM, [BDBU]OH, [ODBU]IM, [[ODBU]OH were synthesized successfully by introducing the alkyl chains of 1‐bromobutane or 1‐bromooctane to 1,8‐diazabicyclo [5.4.0] undec‐7‐ene (DBU), and then, employing imidazole (IM^?) or hydroxide (OH^?) as counter ions. The above obtained four ionic liquids were applied in the synthesis of alcohol ester 12 in isobutyraldehyde (IBD)/aqueous media for the first time. Interestingly, after reaction, production of alcohol ester 12 can be self‐separated from ionic liquids/water (ILs/W) catalytic system automatically. Furthermore, the self‐separated ILs/W can be recycled and used in next catalytic reaction for at least 5 times without obvious loss of catalytic performance. In this work, the structure, purity, thermal stability and alkalinity of DBILs were characterized systematically. [BDBU]IM shows high alkalinity and thus enhances yield of 66.17%. From thermo gravimetric analyzer (TGA), [BDBU]IM also exhibits excellent thermal stability. So [BDBU]IM was chosen for the further studying. Furthermore, quantum chemistry is applied to calculate the interaction forces and electron energies of reactants by DFT, and the calculation results illustrate the feasibility of synthetic process of DBILs. The self‐separation strategy of DBILS in this work may open up a new avenue for the clean synthesis of other industrial products.     

A switchable-oxidative cellulose filter paper bearing immobilized Mn(III)-salen complex for alcohol oxidation

Surface modifications of polysaccharide filter papers can alter their catalytic properties significantly. In particular, polysaccharides have gained increasing interest in the development of heterogeneous catalysts. This wok introduces a new approach to the heterogeneous/ sustainable catalytic system preparation based on a catalytic filter paper modified by silylation followed by immobilization of a Mn(III)-salen complex as a novel “catalytic filtration” or “portable catalysis”. Oxidation of alcohols as well as direct conversion of alcohols to Schiff bases and oximes were performed by filtration and passing the reactants through the modified filter paper. Oxidation of benzyl alcohol in the presence of molecular oxygen and NaOCl, selectively leads to aldehydes and carboxylic acids, respectively. The direct conversion of alcohols to Schiff bases and oximes resulted in the formation of insoluble products on the filter paper. Another advantage of the modified filter paper was its stability and reusability for several times with preservation of the catalytic activity and swellability, which no shrinkage during consecutive wetting–drying cycles was observed. Also, a deep study was conducted over mechanism, reusability/stability, and control experiments of the alcohol oxidation. This study gave new insights into the catalytic propensities of a cellulose filter paper via filtration of reactants.     

RAMA stain: A fast,sensitive and less protein‐modifying CBB R250 stain

SDS‐PAGE and CBB staining are two of the most popular methods used for protein analysis. Although many reports that describe such staining methods have been published, these conventional protocols require several hours or days for staining and de‐staining. In this study we describe a recently developed, fast and sensitive CBB staining method that utilizes the staining solution of RAMA that consists of the low‐cost reagents: CBB R250, acetic acid, methanol and ammonium sulfate, and the destaining solution of water. Our method dose dependently detects 12 nanograms protein within 60 min and with a wide protein spectrum. Although the features of the dose‐dependent relationship depend upon protein amounts and protein types, for most of the protein samples tested, a linear relationship was observed in the region from 12 to 330 ng. Moreover, through further washing, the detection sensitivity of protein is enhanced and reaches a maximum at 1.4 ng and then gradually decreases in the de‐staining process. It has been shown recently through MS analyses that the sensitive colloidal CBB staining methods frequently result in artifactual methylations due to the strong acid and long contact during staining and the destaining processes. Such artifacts were reported to be reduced by the replacement of strong inorganic acid with acetic acid and because RAMA utilizes acetic acid and is in contact with the proteins for a short time during staining and de‐staining, it is expected that in vitro artifacts will be reduced. Finally, MS analyses of RAMA‐stained protein bands were revealed not to have been methylated.     

Full friendly index sets of Cartesian products of two cycles

Let G =（V, E） be a connected simple graph. A labeling f ： V → Z2 induces an edge labeling f＊ ： E → Z2 defined by f＊（xy） = f（x） ＋f（y） for each xy ∈ E. For i ∈ Z2, let vf（i） = ｜f^-1（i）｜ and ef（i） = ｜f＊^-1（i）｜. A labeling f is called friendly if ｜vf（1） - vf（0）｜ ≤ 1. For a friendly labeling f of a graph G, we define the friendly index of G under f by if（G） = e（1） - el（0）. The set [if（G） ｜ f is a friendly labeling of G} is called the full friendly index set of G, denoted by FFI（G）. In this paper, we will determine the full friendly index set of every Cartesian product of two cycles.     

Environmentally friendly surface modification of silk fiber: Chitosan grafting and dyeing

In this paper, the surface modification of silk fiber using anhydrides to graft the polysaccharide chitosan and dyeing ability of the grafted silk were studied. Silk fiber was degummed and acylated with two anhydrides, succinic anhydride (SA) and phthalic anhydride (PA), in different solvents (dimethyl sulfoxide (DMSO) and N,N-dimethyl formamide (DMF)). The effects of anhydrides, solvents, anhydride concentration, liquor ratio (L:R) and reaction time on acylation of silk were studied. The polysaccharide chitosan was grafted to the acylated silk fiber and dyed by acid dye (Acid Black NB.B). The effects of pH, chitosan concentration, and reaction time on chitosan grafting of acylated silk were investigated. The physical properties show sensible changes regardless of weight gain. Scanning electron microscopy (SEM) analysis showed the presence of foreign materials firmly attached to the surface of silk. FTIR spectroscopy provided evidence that chitosan was grafted onto the acylated silk through the formation of new covalent bonds. The dyeing of the chitosan grafted-acylated silk fiber indicated the higher dye ability in comparison to the acylated and degummed silk samples. The mechanism of chitosan grafting over degummed silk through anhydride linkage was proposed. The findings of this research support the potential production of new environmentally friendly textile fibers. It is worthwhile to mention that the grafted samples have antibacterial potential due to the antibacterial property of chitosan molecules.     

Vicious Walkers, Friendly Walkers, and Young Tableaux. III. Between Two Walls

We derive exact and asymptotic results for the number of star and watermelon configurations of vicious walkers confined to lie between two impenetrable walls, as well as corresponding results for the analogous problem of -friendly walkers. Our proofs make use of results from symmetric function theory and the theory of basic hypergeometric series.     

N-油酰基谷氨酸水基润滑添加剂的合成及其摩擦磨损特性研究

将油酸酰氯和谷氨酸在碱性溶液中反应得到N-油酰基谷氨酸,用红外光谱仪对其结构进行表征;用四球摩擦磨损试验机考察了N-油酰基谷氨酸三乙醇胺盐在水溶液中的摩擦磨损性能,并用俄歇电子能谱仪分析其磨斑表面边界膜的化学组成和元素分布.结果表明,当N-油酰基谷氨酸三乙醇胺添加量为0.25%时,其水溶液表现出较好的抗磨和减摩特性.这可能是由于N-油酰基谷氨酸三乙醇胺盐中的极性基团吸附在钢球表面、长碳链疏水性烃基在金属表面形成较厚的保护膜、在较高载荷条件下发生化学反应并形成高强度摩擦化学反应膜的缘故.当添加剂的添加量为2.00%时,N-油酰基谷氨酸三乙醇胺盐的防锈性较好,经细菌性试验表明其具有一定的抗菌能力.     

Stress and Moisture Effects on Thin Film Buckling Delamination

Deposition processes control the properties of thin films; they can also introduce high residual stresses, which can be relieved by delamination and fracture. Tungsten films with high 1–2 GPa compressive residual stresses were sputter deposited on top of thin (below 100 nm) copper and diamond-like carbon (DLC) films. Highly stressed films store large amounts of strain energy. When the strain energy release rate exceeds the films' interfacial toughness, delamination occurs. Compressive residual stresses cause film buckling and debonding, forming open channels. Profiles of the buckling delaminations were used to calculate the films' interfacial toughness and then were compared to the adhesion results obtained from the superlayer indentation test. Tests were conducted in both dry and wet environments and a significant drop in film adhesion, up to 100 times was noticed due to the presence of moisture at the film/substrate interface.     

Targeted Multiresidue Method for the Analysis of Different Classes of Pesticides in Agro-Food Industrial Sludge by Liquid Chromatography Tandem Mass Spectrometry

Sludge generated after washing of fruits and vegetables during agro-food processes is a complex matrix and selective methods for the identification and quantification of pesticides’ residues are necessary in order to achieve a sustainable and effective management of the total sewage. The present work describes the development and validation of a reliable, simple and fast analytical method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the determination of 47 pesticides of different chemical classes, including organosphosphates, pyrethroids, neonicotinoids, triazoles and others, in sludge samples after QuEChERS sample preparation. The necessity of the individual steps of QuEChERS was investigated and the LC-ESI-MS/MS conditions were optimized to achieve maximum sensitivity of the target analytes. The method limits of detection (LODs) ranged between 0.0005 mg/kg (imidacloprid) and 0.05 mg/kg (beta cyfluthrin). The recoveries ranged between 71–120% and the repeatability of the method was ≤25% expressed as relative standard deviation. The method was applied to sludge samples generated after washing of fruits in an agro-fruit-packaging unit in Greece. The results showed the presence of 37 pesticides’ active substances with concentrations ranging from low ppbs, such as fludioxinil (5 μg/kg) up to low ppms such as beta cyfluthrin (3.5 mg/kg) and with their sum concentration reaching up to 19 mg/kg.