Reductive C−C Coupling from α,β‐Unsaturated Nitriles by Intercepting Keteniminates

We present an atom‐economic strategy to catalytically generate and intercept nitrile anion equivalents using hydrogen transfer catalysis. Addition of α,β‐unsaturated nitriles to a pincer‐based Ru?H complex affords structurally characterized κ‐N‐coordinated keteniminates by selective 1,4‐hydride transfer. When generated in situ under catalytic hydrogenation conditions, electrophilic addition to the keteniminate was achieved using anhydrides to provide α‐cyanoacetates in high yields. This work represents a new application of hydrogen transfer catalysis using α,β‐unsaturated nitriles for reductive C?C coupling reactions.     

Splitting tendency of cellulosic fibers. Part 2: Effects of fiber swelling in alkali solutions

The splitting tendency of lyocell fiber in aqueous alkali solutions like KOH, NaOH, LiOH and TMAH was investigated. Up to 5 M concentration of alkali solutions, cation type is important on splitting of lyocell. Above 5 M concentration, cation type is no more relevant to splitting of lyocell. At 1 M of alkali solutions, alkali retention value (ARV) and split number increase in the order of KOH<LiOH<NaOH<TMAH. It was proposed that lyocell is swollen homogeneously inside fiber above 5 M alkali concentration, so that when force is applied on fiber, no split occurs in lyocell fiber since there isn’t enough internal stress inside of the fiber. Different concentrations of each type of alkali result in the same ARV for the fiber, but their alkali distribution inside fiber is the decisive point for splitting of lyocell fiber, so that for each alkali type different split numbers are observed. Depending on alkali concentration and alkali type, maximum splitting of a fiber into 15–20 fibrils could be observed.     

Inter-laboratory comparison scheme for fuel sector, LABKAR in Turkey

Fuel sector is one of the powerful sectors in Turkish industry. The implementation of a new law for regulating the fuel sector had enforced the quality control of fuels sold to public. This resulted in several accredited fuel-testing laboratories to emerge. Thus, a scheme to evaluate their proficiency in measurements became an important requirement. The inter-laboratory comparison scheme LABKAR for gasoline, diesel oil, LPG, lubricating oil and biodiesel samples have evolved to fulfill this need. In this paper, LABKAR is introduced; the results obtained from the program are analyzed and discussed. The kernel densities of the participants’ results show that the use of robust mean as a consensus value is appropriate for fuel samples. Although the number of rounds is not enough to derive strict conclusions, it is seen that the performance of the scheme based on the standard deviations and coefficient of variations is improving in each round. It has been observed that the number of laboratories receiving “action” or “warning” is decreasing, which indicates that they are benefiting from the scheme.     

Self-Tuning GMV Control of Glucose Concentration in Fed-Batch Baker’s Yeast Production

A detailed system identification procedure and self-tuning generalized minimum variance (STGMV) control of glucose concentration during the aerobic fed-batch yeast growth were realized. In order to determine the best values of the forgetting factor (λ), initial value of the covariance matrix (α), and order of the Auto-Regressive Moving Average with eXogenous (ARMAX) model (n _a, n _b), transient response data obtained from the real process wereutilized. Glucose flow rate was adjusted according to the STGMV control algorithm coded in Visual Basic in an online computer connected to the system. Conventional PID algorithm was also implemented for the control of the glucose concentration in aerobic fed-batch yeast cultivation. Controller performances were examined by evaluating the integrals of squared errors (ISEs) at constant and random set point profiles. Also, batch cultivation was performed, and microorganism concentration at the end of the batch run was compared with the fed-batch cultivation case. From the system identification step, the best parameter estimation was accomplished with the values λ?=?0.9, α?=?1,000 and n _a?=?3, n _b?=?2. Theoretical control studies show that the STGMV control system was successful at both constant and random glucose concentration set profiles. In addition, random effects given to the set point, STGMV control algorithm were performed successfully in experimental study.     

Poly(Aryl ethers) by nucleophilic aromatic substitution. II. Thermal stability

The thermal stability and degradation process for a specific poly(aryl ether) system have been studied. In particular, the polymer which is available from Union Carbide Corporation as Bakelite polysulfone has been examined in detail. Polysulfone can be prepared from 2,2-bis(4-hydroxyphenyl)propane and 4,4′-dichlorodiphenyl sulfone by nucleophilic aromatic substitution. Because of a low-temperature transition at ? 100°C. and a glass transition at 195°C., polysulfone retains useful mechanical properties from ?100°C. to 175°C. A number of experimental methods were utilized to study the thermal decomposition process for this polymer system. Polysulfone gradually degraded in vacuum above 400°C. as demonstrated by mass spectrometry. Thermogravimetric analysis in argon, air, or high vacuum indicated that rapid decomposition began above 460°C. From gas chromatography, mass spectrometry and repeated laboratory pyrolyses, a number of products from polymer decompositions were identified. The most important degradation process in vacuum or inert atmosphere was loss of sulfur dioxide. Several model compounds representative of portions of poly(aryl ether) molecules were synthesized and the relative thermal stabilities determined. Possible mechanisms for pure thermal decomposition of polysulfone were derived from the product analyses, model studies, and consideration of bond dissociation energies.