Aliphatic Polyester/polyhedral Oligomeric Silsesquioxanes Hybrid Networks via Copper‐free 1,3‐dipolar Cycloaddition Click Reaction

In this study, we describe the preparation and characterization of a new class of thermoset hybrid networks containing aliphatic polyester and polyhedral oligomeric silsesquioxanes (POSS). The copper‐free 1,3‐dipolar cycloaddition click reaction of internal alkyne functionalized aliphatic polyester and multifunctional azido POSS with different concentrations led to highly crosslinked thermoset networks. The click reactions performed under ambient conditions (i.e., in tetrahydrofuran at room temperature for 1 day) in the absence of any catalyst. The chemical composition of hybrid networks and homogenous distribution of POSS molecules were confirmed by Fourier transform infrared spectroscopy and scanning electron microscopy with energy dispersive spectroscopy. The swelling ratios of hybrid networks were commonly decreased by increasing POSS‐N₃ content and by changing polar solvents to apolar solvents. Thermogravimetric analysis results demonstrated that the thermal stability of hybrid networks increased with higher POSS feeding ratio. Tensile tests were applied to evaluate the mechanical properties of hybrid networks. Compared to neat aliphatic polyester, the mechanical properties of hybrid networks significantly improved. For instance, the tensile strength were enhanced from 5 MPa to 19 MPa by increasing the concentration of azido functionalized POSS from 10 to 40. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2222–2227     

Detecting organic vapors using a conductometric sensor prepared from Ardel®D-100 and graphite

The composites of graphite with Ardel^?D-100 which is a trademark of a polyester of bisphenol-A with terephthalic and isophthalic acid were used as a sensing material in a conductometric vapor sensor. The magnitudes of responses are increased in the order of benzene, isobutyl acetate, isoamyl acetate, ethyl benzene and chloro benzene. This suggests that Ardel^?D-100 can be used as a sensing material for chlorobenzene, ethyl benzene and isoamyl acetate. On the other hand, specific retention volumes of the sensed vapors on Ardel^?D-100 coated on graphite were determined by inverse gas chromatography at temperatures between 200 and 260 °C. The distribution coefficient, K _s of the vapors between stationary and mobile phases in the column was obtained. It was revealed for the first time that the logarithm of K _s of the solvents varies almost linearly with their responses based on conductometric resistance of the sensing polymer composite. Subsequently, the study suggests that gas chromatographic retention data can be used in prediction of the conductometric responses of a polymeric sensor to vapors. Correspondence: Ferdane Karaman, Department of Chemistry, Yildiz Technical University, 34220 Istanbul-Esenler, Turkey     

Biomimetic Approaches for Membrane Technologies

Membrane technology is the dominant process in water treatment. However, the operation cost of membranes cannot be decreased unless the amount of fouling, the “Achilles heel” of membranes, and energy consumed are cut. The high energy requirements in commercial nanofiltration, reverse osmosis and forward osmosis technologies lead researchers to develop new membrane designs having high flux values with high salt rejection values. The purpose of this review is to present the inadequacies of the membrane processes by considering studies related to fouling and energy minimization. In this respect, lipid bilayers, block copolymers, aquaporin Z proteins and aligned carbon nanotubes can be the base to build biomimetic membranes. Such studies are summarized due to their remarkable properties in fouling control. Furthermore, the review describes the membrane design strategies and points the limitations hindering commercialization. Additionally, it is hoped that this review will trigger further needed studies.     

Formal synthesis of (+)-neooxazolomycin via a Stille cross-coupling/deconjugation route

A formal synthesis of neooxazolomycin is described via the preparation of Kende’s key intermediate in a longest linear sequence of 23 steps. This work is founded upon the union of three fragments: Moloney’s lactam-derived triflate, a vinyl stannane and a Julia-Kocienski sulfone and encompasses three key steps: (i) a Stille cross-coupling to combine the triflate and vinyl stannane, (ii) a base-promoted enone deconjugation to derive the dihydroxylation precursor and (iii) our previously reported Julia-Kocienski methodology to assemble the pentadienyl amine side chain with the sulfone precursor.     

Preconcentration of cadmium and nickel using the bioadsorbent Geobacillus thermoleovorans subsp. stromboliensis immobilized on Amberlite XAD-4

Cadmium and nickel ions have been preconcentrated on Geobacillus thermoleovorans subsp. stromboliensis, immobilized on Amberlite XAD-4, and were determined by flame atomic absorption spectrometry (FAAS). Parameters such as pH, amount of adsorbent, eluent type and volume, flow rate of solution and the matrix interference effect on retention have been studied, and extraction conditions were optimized. Elution of Cd(II) and Ni(II) from minicolumns was carried out with 1.0 M hydrochloric acid or nitric acid with recoveries from 97 to 100%. The sorption capacity is 0.0373 and 0.0557 mmol g^?1 for Cd(II) and Ni(II), respectively. The detection limits were 0.24 μg L^?1 for cadmium and 0.3 μg L^?1 for nickel. The relative standard deviations of the procedure were below 10%. The procedure was validated by analyzing certified reference materials and applied to the determination of Cd(II) and Ni(II) in natural water and food samples.     

Zirconium Catalyzed Ethylene Oligomerization

A review of the scientific and patent literature on oligomerization of ethylene to linear olefins in the presence of homogenous or heterogeneous zirconium complexes and various aluminum organic compounds has been fulfilled for last twenty-five years. Over these years, a wide range of studies had been conducted for selective oligomerization of ethylene into a narrow fraction of linear α-olefins such as C₄-C₈ and C₆-C₁₀ fractions. During the discussion of these catalytic systems, exceptional attention is also paid to feature works such as the activity of the catalysts and the acquisition of clear liquid product without any trace of polymer, all of which play important roles in the selection of the best technology.     

Pyridinedithioesters as heterodienophiles: application to the synthesis of aprikalim

[reaction: see text] Pyridinedithioesters can be used as efficient heterodienophiles when activated by complexation with BF(3), by protonation, or by oxidation of the nitrogen atom of the pyridine moiety. The hetero-Diels-Alder reaction using 3-pyridinedithioester as a heterodienophile was the key step in a new synthesis of Aprikalim in racemic form. The methodology can be reliably extended to prepare new analogues of Aprikalim.     

Barrier height enhancement of metal/semiconductor contact by an enzyme biofilm interlayer

A metal/interlayer/semiconductor (Al/enzyme/p-Si) MIS device was fabricated using α-amylase enzyme as a thin biofilm interlayer. It was observed that the device showed an excellent rectifying behavior and the barrier height value of 0.78?eV for Al/α-amylase/p-Si was meaningfully larger than the one of 0.58?eV for conventional Al/p-Si metal/semiconductor (MS) contact. Enhancement of the interfacial potential barrier of Al/p-Si MS diode was realized using enzyme interlayer by influencing the space charge region of Si semiconductor. The electrical properties of the structure were executed by the help of current–voltage and capacitance–voltage measurements. The photovoltaic properties of the structure were executed under a solar simulator with AM1.5 global filter between 40 and 100?mW/cm² illumination conditions. It was also reported that the α-amylase enzyme produced from Bacillus licheniformis had a 3.65?eV band gap value obtained from optical method.     

Morphology and thermal characterization of montmorillonite/polybenzimidazole nanocomposite

In this study, thermal and morphological properties of organically modified montmorillonite (mMMT)/poly(2,5-benzimidazole) (ABPBI) composite were investigated. The morphology and structure of mMMT/ABPBI composites were characterized by infrared, X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis techniques. At low mMMT loading levels, exfoliation was the predominant mechanism of mMMT dispersion. At high mMMT loading levels, nonintercalated microcomposite morphology is partially favored in expense of the intercalated nanocomposite. Thermal degradation of nanocomposite occured in three stages. In the second stage of thermal degradation, the onset temperature of degradation for the mMMT/ABPBI nanocomposites was lower than that of ABPBI polymer. In the last stage, the improvement in thermal stability by the introduction of mMMT into the ABPBI was different from the second stage. The activation energy for degradation of ABPBI increased from 62.6 to 77.7 kJ mol^?1 after loading of 5 mass% of mMMT into ABPBI matrix under air atmosphere.