Poly(paraphenylene sulfide) and Poly(metaphenylene sulfide) via Light‐Initiated SRN1‐Type Polymerization of Halogenated Thiophenols

In this work, the synthesis of various halogenated thiophenol derivatives is presented. These thiophenols are used as monomers in light‐initiated S_RN1‐type radical polymerization reactions. The method provides easy access to industrially relevant poly(paraphenylene sulfide) and poly(metaphenylene sulfide). The influence of the halide leaving group and of other substituents in the thiophenol monomer on the polymerization process is investigated.

     

Production of Raw Starch-Saccharifying Thermostable and Neutral Glucoamylase by the Thermophilic Mold <Emphasis Type="Italic">Thermomucor indicae-seudaticae</Emphasis> in Submerged Fermentation

Among physical and nutritional parameters optimized by “one variable at a time” approach, four cultural variables (sucrose, MgSO₄ ^.7H₂O, inoculum size, and incubation period) significantly affected glucoamylase production. These variables were, therefore, selected for optimization using response surface methodology. The p-values of the coefficients for linear effect of sucrose and inoculum size were less than 0.0001, suggesting them to be the key experimental variables in glucoamylase production. The enzyme production (34 U/ml) attained under optimized conditions (sucrose, 2%; MgSO₄ ^.7H₂O, 0.13%; yeast extract, 0.1%; inoculum size, 5 × 10⁶ spores per 50 ml production medium; incubation time, 48 h; temperature, 40°C; and pH 7.0) was comparable with the value predicted by polynomial model (34.2 U/ml). An over all 3.1-fold higher enzyme titers were attained due to response surface optimization. The experimental model was validated by carrying out glucoamylase production in shake flasks of increasing capacity (0.25–2.0 l) and 22-l laboratory bioreactors (stirred tank and airlift), where the enzyme production was sustainable. Furthermore, the fermentation time was reduced from 48 h in shake flasks to 32 h in bioreactors.     

Chemometric analysis of disubstituent effects on the 13C chemical shifts of the carboxyl carbons (deltaCO) of benzoic acids. A comparative study of the substituent effects on the strength of benzoic acids in apolar aprotic media

The results of measurements of substituent induced chemical shifts of carboxyl carbons (deltaCO) of dichloro- and difluorobenzoic acids, including the monosubstituted ones with substituents at meta- and/or ortho- positions, in chloroform-d and strengths of these acids (log K) in chlorobenzene show an anomalous reverse trend between deltaCO and log K, while the electron density at carboxyl carbons should influence similarly both deltaCO and log K. A detailed chemometric analysis of comparison of disubstituent effects between deltaCO and log K on the basis of Fujita-Nishioka's multiparameter approach and assumption of additivity of substituent effects shows a dominance of the localized pi-polarization mechanism relative to simple electrostatic effects upon deltaCO. Further, steric factors play a significant role in determining deltaCO whereas with respect to log K they were insignificant. The overall anomaly has been rationalized keeping in mind that, while log K is a gross measure of energy differences between the ionized and unionized forms of the acids, deltaCO is a very sensitive probe for determining changes in electron density at the carboxyl carbon of the unionized acid.     

Optimization of critical medium components for the maximal production of gentamicin by Micromonospora echinospora ATCC 15838 using response surface methodology

Optimization of the fermentation medium components for maximum gentamicin production by Micromonospora echinospora ATCC 15838 was carried out. Response surface methodology was applied to optimize the medium constituents. A 2⁴full-factorial central composite design was chosen to explain the combined effects of the four medium constituents, viz. starch, soyabean meal, K₂HPO₄, and CoCl₂ and to design a minimum number of experiments. A second order model was developed and fitted using least square method. The R ² value of the model was 0.9723, which shows that model is best fit for the present studies. The results of analysis of variance and regression of a second order model showed that the linear effects of starch (p<0.001697) and CoCl₂(p<7.99E-13), and cross product effects of starch and soyabean meal (p<0.029876) and soyabean meal and CoCl₂ (p<0.008909) were more significant, suggesting that these were critical variables having the greatest effect on the production of gentamicin in the production medium. The optimized medium consisting of 9 g/L starch, 3 g/L soyabean meal, 0.9 g/L K₂HPO₄, and 0.01 g/L CoCL₂ predicted 850 mg/L of gentamicin which was almost 110% higher than that of the unoptimized medium. The amounts of starch, soyabean meal, and K₂HPO₄ required were also reduced with RSM.     

Combinatıon of a Box-Behnken design technique with response surface methodology for optimization of the photocatalytic mineralization of C.I. Basic Red 46 dye from aqueous solution

The photodegradation of an industrial azo dye C.I Basic Red 46 was examined in a fixed-bed photoreactor using UV-lamps simulated to the solar irradiation. In our photodecolorization study, the UV/TiO₂ process was optimized using the Box-Behnken approach to evaluate the synergistic effects of three independent parameters (initial concentration of the dye, flow rate, and UV intensity) on mineralization effectiveness. The response surface methodology was in good promise with the prediction model (coefficients of determination of decolorization and mineralization were R²_Dec = 0.997 and R²_TOC = 0.994, respectively). The effects of the factors could be estimated from a second–order polynomial equation and student’s t-test. The optimal parameters of decolorization and mineralization were as follows: initial concentration of colorant 25 mg L⁻¹, rate of fluid flow 0.3 L min⁻¹, and ultraviolet light intensity 38.1 W m⁻². The decolorization and mineralization removal efficiency under these optimal conditions were 100% and 57.63% respectively. These results indicate that optimization using response surface methodology, based on the Box-Behnken approach, is an excellent tool for determining the optimal conditions, and the process can be easily extrapolated for a specific treatment of real waste water containing the azo dye C.I Basic Red 46. Also, the intermediates that were produced during photodegradation process of Basic Red 46 were determined by GC/MS.     

Optimization of alkaline protease production by Bacillus sp. using taguchi methodology

Optimization of alkaline protease production parameters by Bacillus sp. was investigated using Taguchi methodology. The pH of the medium was observed to be the most significant factor among all selected optimization parameters at an individual level. The combinatorial influence of least significant factors, inoculum level and salt solution concentration (at the individual level), resulted in an interacting severity index of 76%, suggesting their interactive role in the regulation of protease production in this microbial species. Protease production could be improved more than 100% with Taguchi’s optimized conditions of the medium composition by this microorganism.     

Preparation of vinylphenols from 2- and 4-hydroxybenzaldehydes

A straightforward, high-yielding procedure has been developed for the manufacture of substituted vinylphenols from 2- and 4-hydroxybenzaldehydes utilising classical Knoevenagel condensation reaction conditions.     

Ab initio calculations of vibronic activity in phosphorescence microwave double resonance spectra of p-dichlorobenzene

The phosphorescence spectrum of p-dichlorobenzene has been calculated using multiconfiguration self-consistent-field wave functions and the quadratic response technique. Attention has been paid to the intensity distribution of the singlet–triplet (³B_1u¹A_g) transition through a number of vibronic subbands. The second order spin–orbit coupling (SOC) contribution to the spin splitting of the ³B_1u (^3*) state is found to be almost negligible, and the calculations therefore provide a good estimate for the zero-field splitting (ZFS) parameters based only on the electron spin–spin coupling expectation values. Nuclear quadrupole resonance constants for the different Cl isotopes are also calculated to accomplish the ZFS assignment. The electric dipole activity of the spin sublevels in the triplet–singlet transitions to the ground-state vibrational levels is estimated by calculations of derivatives using distorted geometries which are shifted from the equilibrium position along different vibrational modes. A vibrational analysis of the phosphorescence spectrum, based on the SOC-induced mixing of the singlet and triplet states calculated along different vibrational modes, provides reasonable agreement with experimental data.Acknowledgment O. R.-P. would like to thank the European MOLPROP network for support. The authors thank Alexander Baev for fruitful discussions. This work was supported by the Swedish Royal Academy of Science (KVA).     

Combinatorial analysis of Tetris-like games

We study some combinatorial properties of Tetris-like games by using Schützenberger methodology and probability generating functions. We prove that every Tetris-like game is equivalent to a finite state automaton and propose a straight foward algorithm to transform a Tetris-like game into its corresponding automaton. In this way, we can study the average number of pieces inserted during a game and the average score as a function of the player's ability and the pieces extrusion.     

Making decisions in the absence of clear facts

Bennis and O’Toole [Bennis, W.G., O’Toole, J., 2005. How business schools lost their way. Harvard Business Review 83, 96–104] have recently argued that decision makers need guidance in ‘making decisions in the absence of clear facts’. As such, decision makers must be able to resourcefully use whatever limited information is available and advantageously portray its implications. Based on recently published theory which directly addresses this requirement, this paper demonstrates, through a practical example, how decision makers can make systemic decisions in situations characterized by extremely limited information and, furthermore, what form such decisions can take. Evidence is provided, therefore, that operational research can effectively address what appears to be a gap in management training.