Metallopolymers based on a polyazomethine ligand containing rigid oxadiazole and flexible tetramethyldisiloxane units

Soluble, easily processable polymer–metal complexes with improved optical and dielectric properties for optoelectronic functional materials were obtained. For this, a new polyazomethine (PAZ2) was prepared by the reaction of a siloxane dialdehyde and bis(formyl‐p‐phenoxymethyl) tetramethyldisiloxane with 2,5‐bis(p‐aminophenyl)‐1,3,4‐oxadiazole, and it was used as a ligand for Cu(II), Co(II), and Zn(II) ions on the basis of the presence of the electron‐donor nitrogen atoms from the azomethine group and oxadiazole ring. The structure of the PAZ2 was determined by spectral [Fourier transform infrared (FTIR) and ¹H‐NMR spectroscopy] techniques. The metal complexation was proven by FTIR spectroscopy, and the silicon‐to‐metal ratios in the complexes were established by energy‐dispersive X‐ray fluorescence. The new materials were characterized by gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry. The optical properties of PAZ2 and the derived metal complexes were studied by ultraviolet–visible and fluorescence spectroscopies. PAZ2 shows fluorescence emission, and it was significantly enhanced by metal complexation. The emission was enhanced by protonation; this behavior is useful, especially for sensors. The electrical properties were investigated by dielectric spectroscopy at various frequencies and temperatures, and this emphasized the existence of dipolar relaxations. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41631.     

Dynamic mechanical behaviour of random copolymers of a LC-methacrylate and octyl methacrylate

The dynamic mechanical behaviour of random copolymers of LC monomer-1-(hexyloxycarbonyl)ethyl 4-[4-(methacryloyloxy)benzoyloxy]benzoate (HB) and octyl methacrylate (OMA) was studied in the main transition and flow regions. Even though the aliphatic end groups of the side chain of HB and OMA are roughly the same, the T _g temperature of poly(HB) is ∼ 80 K higher than that of poly(OMA); this fact is due to the presence of the stiff phenyl benzoate mesogenic group in the side chain of HB. With increasing content of OMA in the copolymer the superimposed curves of the storage G′ _p and loss G′′ _p moduli at a constant temperature shift towards shorter frequencies. It has been shown that this shift is mainly due to an increase of the free volume in the copolymers with increasing content of OMA. While HB monomer shows liquid crystalline (LC) properties, its polymer (poly(HB)) and random copolymers with OMA show only isotropic thermal behaviour because no flexible spacer is present in the side chain of HB which would decouple the main chain and mesogenic group motions. This means that neither the homopolymer of HB, nor its copolymers with a flexible comonomer retain the LC properties of the starting LC monomer, HB. Received: 26 September 1996/Revised: 7 November 1996/Accepted: 7 November 1996     

Chemical stability of some poly(amide imide) type polymers

The stability of some heterocyclic poly(amide imide)s in acidic and alkaline medium was compared to the structurally related polyimide and poly(amide imide)s without other heterocyclic groups. All the polymers have high stability in acidic medium. The introduction of additional heterocycles such as 1,3,4-0xadiazole or phenylquinoxaline into the macromolecular chain of a poly(amide imide) increases substantially the resistance to alkaline medium. Polyamides containing imide rings only in the side chain are more stable to hydrolysis than related polyamide having imide units in the main chain.     

Processing parameters of the diethylenetriamine and unsaturated aldehyde resin

The dependence of processing parameters of the reaction between diethylenetriamine (DETA) and crotonaldehyde (CR) or cinnamaldehyde (CA) on reaction time were followed by calorimetric and viscosity measurements. Resins with molecular weights up to 800 g/mol and content of unreacted monomers under 1% were formed. The most reactive were the amino and aldehyde groups. The aldehyde groups are five times more reactive than double bonds. ? NHCHOH, ? CH₂NH? , ? CHNH? , and ? N?CH? groups were formed. The rates of the reactions and the rate constants decrease with increasing molar ratio between DETA and unsaturated aldehydes. The heat of the addition of DETA to CR was up to 54 KJ/mol and the total heat of reaction was up to 71 KJ/mol. The heat of addition of DETA to CA was up to 32 KJ/mol and the total heat of reaction was up to 61 KJ/mol. For DETA and CR the activation energy of condensation were 57.3 KJ/mol, and 42.0 KJ/mol for DETA and CA. The viscosity of the final products increased up to hard resins.     

A review of biodiesel production by integrated reactive separation technologies

Biodiesel is a biodegradable and renewable fuel, emerging as a viable alternative to petroleum diesel. Conventional biodiesel processes still suffer from problems associated with the use of homogeneous catalysts and the limitations imposed by the chemical reaction equilibrium, thus leading to severe economic and environmental penalties. This work provides a detailed review—illustrated with relevant examples—of novel reactive separation technologies used in biodiesel production: reactive distillation/absorption/extraction, and membrane reactors. Reactive separation offers new and exciting opportunities for manufacturing the fatty acid alkyl esters involved in the industrial production of biodiesel and specialty chemicals. The integration of reaction and separation into one operating unit overcomes equilibrium limitations and provides major benefits such as low capital investment and operating costs. These reactive separation processes can be further enhanced by heat‐integration and powered by heterogeneous catalysts, to eliminate all conventional catalyst related operations, using efficiently the raw materials and the reaction volume, while offering higher conversion and selectivity, as well as significant energy savings compared with conventional biodiesel processes. Remarkable, in spite of the high degree of integration, such integrated reactive‐separation processes are still very well controllable as illustrated by the included examples. Copyright © 2012 Society of Chemical Industry     

Dynamic optimization of a dividing-wall column using model predictive control

Dividing-wall column (DWC) is one of the best examples of process intensification, as it can bring significant reduction in the capital invested as well as savings in the operating costs. Conventional ternary separations progressed from the (in-)direct sequences to thermally coupled columns such as Petlyuk configuration, and later to the DWC compact design that integrates the two distillation columns into a single shell. Nevertheless, this integration leads also to changes in the control and operating mode due to the higher number of degrees of freedom.In this work we explore the dynamic optimization and advanced control strategies based on model predictive control (MPC), coupled or not with PID. These structures were enhanced by adding an extra loop controlling the heavy component in the top of the feed side of the column, using the liquid split as manipulated variable, thus implicitly achieving energy minimization. To allow a fair comparison with previously published references, this work considers as a case-study the industrially relevant separation of the mixture benzene–toluene–xylene (BTX) in a DWC.The results show that MPC leads to a significant increase in performance, as compared to previously reported conventional PID controllers within a multi-loop framework. Moreover, the optimization employed by the MPC efficiently accommodates the goal of minimum energy requirements – possible due to the addition of an extra loop – in a transient state. The practical benefits of coupling MPC with PID controllers are also clearly demonstrated.     

A surface-enhanced Raman spectroscopy study of thin graphene sheets functionalized with gold and silver nanostructures by seed-mediated growth

We describe a simple method for decorating graphene (1–5 layers) with Au and Ag nanostructures (nanoparticles, nanorods, and nanoplates). We deposit graphene electrostatically from highly-oriented pyrolytic graphite onto Si/SiO₂ surfaces functionalized with (aminopropyl)trimethoxysilane and grow the metal nanostructures by a seed-mediated growth method from hexanethiolate-coated Au monolayer-protected cluster “seeds” that are attached to graphene by hydrophobic interactions. Scanning electron microscopy reveals the selective growth of Au or Ag nanostructures on the graphene surface. In the case of Au, the low pH 2.8 growth solution causes etching of the graphene and formation of scroll-like structures. For Ag, the high pH 9.3 solution does not seem to affect the graphene. Raman spectroscopy is consistent with the graphene morphology and reveals that the presence of Au and Ag nanostructures increases the Raman scattering from the graphene by a factor of about 45 and 150, respectively. This work demonstrates a simple method for decorating graphene with noble metal nanostructures that may have interesting optical, electronic, and chemical properties for applications in nanoelectronics, sensing, and catalysis.     

Aging effect of atmospheric pressure plasma jet treated polycaprolactone polymer solutions on electrospinning properties

In previous work, an atmospheric pressure plasma jet was applied to successfully improve the electrospinnability of poly-ε-caprolactone (PCL) which enabled the fabrication of beadless nanofibers. In this paper, we report the aging effect of the plasma treatment to evaluate the robustness of the developed process. For this purpose, plasma-treated PCL polymer solutions with different exposure time were stored for 1 and 8 days and the aged solutions were analyzed in terms of conductivity, viscosity, surface tension, pH, and polymer molecular weight. During storage, the surface tension and acidity of the plasma-treated solutions were maintained constant. However, the viscosity was found to be significantly lower after 8 days which was attributed to PCL degradation. Electrospinning of all stored PCL solutions resulted in the generation of beadless PCL nanofibers. The plasma treatment effects were thus found to be highly stable over time and capable of producing high-quality PCL nanofibers up to 8 days. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48914.     

Cloning and heterologous expression of three type II PKS gene clusters from Streptomyces bottropensis

Mensacarcin is a potent cytotoxic agent isolated from Streptomyces bottropensis. It possesses a high content of oxygen atoms and two epoxide groups, and shows cytostatic and cytotoxic activity comparable to that of doxorubicin, a widely used drug for antitumor therapy. Another natural compound, rishirilide A, was also isolated from the fermentation broth of S. bottropensis. Screening a cosmid library of S. bottropensis with minimal PKS-gene-specific primers revealed the presence of three different type II polyketide synthase (PKS) gene clusters in this strain: the msn cluster (mensacarcin biosynthesis), the rsl cluster (rishirilide biosynthesis), and the mec cluster (putative spore pigment biosynthesis). Interestingly, luciferase-like oxygenases, which are very rare in Streptomyces species, are enriched in both the msn cluster and the rsl cluster. Three cosmids, cos2 (containing the major part of the msn cluster), cos3 (harboring the mec cluster), and cos4 (spanning probably the whole rsl cluster) were introduced into the general heterologous host Streptomyces albus by intergeneric conjugation. Expression of cos2 and cos4 in S. albus led to the production of didesmethylmensacarcin (DDMM, a precursor of mensacarcin) and the production of rishirilide A and B (a precursor of rishirilide A), respectively. However, no product was detected from the expression of cos3. In addition, based on the results of isotope-feeding experiments in S. bottropensis, a putative biosynthesis pathway for mensacarcin is proposed.     

Elevated temperature impact on performance of Low Temperature Co-fired Ceramic dielectrics

The need for electronics to operate at temperatures of 200°C and above continues to grow. These applications include avionics, aerospace, automotive, downhole drilling, mining, and many others. To satisfy this demand, a significant amount of research and development has been conducted. Despite the efforts, the number of new electronic components designed specifically for high-temperature operation is still relatively limited. In Low Temperature Co-fired Ceramic (LTCC) packages, LTCC materials are generally used as the host media for a number of pre-fabricated semiconductor components. As a result, reliability of the entire LTCC package largely depends on the performance of the least robust component. Ferro A6M-E and Ferro L8 are the two well-established and recognized LTCC dielectrics widely used for mid and high frequency LTCC applications, including several high reliability aerospace and defense applications that require demanding Mil-Spec qualifications. This study is our first attempt to characterize and understand basic high-temperature dielectric properties of these two commercial LTCC materials. The secondary objective is to initiate a dialogue in attempt to establish reliability requirements for LTCC packages dedicated for high-temperature operation.