Oligoaniline intermediates in the aniline-peroxydisulfate system

Chemical oxidative polymerization of aniline using peroxydisulfate oxidant in aqueous pH 2.5–10.0 buffers yields electrically insulating brown powders that are believed to be mixtures of Michael-type adducts of benzoquinone monoimine and aniline at various stages of hydrolysis. A spectroscopically similar product is formed when solid 1,4-benzoquinone is added to an aqueous solution of aniline at room temperature in the absence of peroxydisulfate. This suggests that the peroxydisulfate oxidant in the aniline/S₂O₈^2? system provides a pathway for the formation of benzoquinone monoimine as an intermediate. Benzoquinone monoimine intermediate could be formed as a result of a Boyland–Sims rearrangement of aniline proceeding via the intermediacy of p-aminophenyl sulfate. Benzoquinone monoimine undergoes a series of conjugate 1,4-Michael-type addition/reoxidation/coupling steps with aniline or p-aminophenyl sulfate yielding the oligoaniline product. The precipitate that is isolated is also in the midst of two simultaneous pH dependent hydrolysis reactions: (i) hydrolysis of the imine groups to quinone, and (ii) hydrolysis of arylsulfates to phenols. The ratio of hydrolysis in each case was determined by the C/N ratio and sulfur elemental analysis values yielding analytical data that is consistent with experimentally determined values and also with our proposed reaction scheme. These findings offer a rationale for the high C/N ratios (>6.0) frequently observed in these systems while tracing the genesis of the residual sulfur in the product to unhydrolyzed arylsulfate. The oligoaniline product has previously been reported to have a novel poly-aza structure consisting of continuously linked –N–N–N– bonds, and alternately also reported to consist of phenazine-type linkages. This study is consistent with the latter and describes a pathway to phenazine coupling through a second and third stage hydrolysis of the arylsulfate and reoxidation with peroxydisulfate. There is no pathway for the formation of linear –N–N–N– linkages in the aniline/benzoquinone adduct and the striking similarity between its spectroscopic properties and the aniline/S₂O₈^2? adduct suggests that it is not a preferred pathway under these experimental conditions.     

Effects of various hydrocarbons on micellar growth

The effect of aliphatic and aromatic hydrocarbons on surfactant micellar growth has been investigated by viscosity measurements at 40°C. Aqueous and aqueous KBr (0.1 M) solutions of 0.1 M cetylpyridinium bromide (CPB) showed that the viscosity behavior changed substantially in the presence of KBr. This is attributed to favorable conditions produced by KBr that assist micellar growth by addition of hydrocarbons. Reasons for the effectiveness of the solubilized hydrocarbons are suggested and supported by theoretical arguments. The causes of viscosity decrease at higher aromatic hydrocarbon concentrations are also explained. Micellar growth with soluble aromatic/aliphatic hydrocarbons could also be initiated if a moderate salt concentration is present in CPB micellar solutions. The chainlength, solubilization site, and molar volume of the soluble hydrocarbons all affect the bulk viscosity of the solution. Such surfactant and hydrocarbon combinations may find use in micellar-enhanced ultrafiltration of benzene and its derivatives, but it should be kept in mind that micellar shape may change and be more curved at higher benzene derivative concentrations.     

On the solution and applicability of bivariate population balance equations for mixing in particle phase

New benchmarks are used to test two classes of discretization methods available in the literature to solve bivariate population balance equations (2-d PBEs), and the applicability of these mean-field equations to finite size systems. The new benchmarks, different from the extensions of their 1-d counterparts, relate to prediction of kinetics of mixing in particle phase under: (i) pure aggregation of particles, called aggregative mixing, and (ii) simultaneous breakup and coalescence of drops. The discretization methods for 2-d PBEs, derived from the widely used 1-d solution methods, are first classified into two classes. We choose one representative method from each class. The results show that the extensions based on minimum consistency of discretization perform quite well with respect to both the new and the old benchmarks, in comparison with the geometrical extensions of 1-d methods. We next revisit aggregative mixing using Monte-Carlo simulations. The simulations show that (i) the time variation of the extent of mixing in finite size systems has power law scaling with the system size, and (ii) the mean-field PBEs fail to capture the evolution of mixing for reduced population of particles at long times. The sum kernel limits the applicability of PBEs to substantially larger particle populations than that seen for the constant kernel. Interestingly, these populations are orders of magnitude larger than those at which the PBEs fail to capture the evolution of total particle population correctly.     

A near infrared optical reflector using one-dimensional photonic crystal structure containing chalcogenide glasses

The reflectivity of one-dimensional chalcogenide photonic crystal (CGPC) structure with the first order reflection band in near infrared (NIR) region is theoretically studied. Sb-Se and Ge-S chalcogenide glasses are used as high and low refractive index layers respectively, because these materials have zero absorption in NIR region. The transfer matrix method (TMM) is employed to calculate the reflective spectra of the proposed structure. The theoretical results of reflective spectra of bulk chalcogenide materials with the composition of Sb₄₀Se₆₀ and Ge₃₀S₇₀ for 4, 8, 12 and 15 layers and thicknesses of 117 nm and 183 nm respectively, at normal incidence, are close agreement with the experimental results. Furthermore, by increasing the number of layers of Sb₄₀Se₆₀ and Ge₃₀S₇₀, the reflection bands can be enhanced in the wider range of the NIR region for the polarization at different angles and thus the broadband omnidirectional reflector can be designed.     

Supersonic Nozzle Flow Simulations for Particle Coating Applications: Effects of Shockwaves,Nozzle Geometry,Ambient Pressure,and Substrate Location upon Flow Characteristics

Characteristics of supersonic flow are examined with specific regard to nano-particle thin-film coating. Effects of shockwaves, nozzle geometry, chamber pressure, and substrate location were studied computationally. Shockwaves are minimized to reduce fluctuations in flow properties at the discontinuities across diamond shock structures. Nozzle geometry was adjusted to ensure optimal expansion (i.e., P _exit = P _ambient), where shock formation was significantly reduced and flow kinetic energy maximized. When the ambient pressure was reduced from 1 to 0.01316 bar, the nozzle’s diverging angle must be increased to yield the optimum condition of minimized adversed effects. Beyond some critical distance, substrate location did not seem to be a sensitive parameter on flow characteristics when P _amb = 0.01316 bar; however, overly close proximity to the nozzle exit caused flow disturbances inside the nozzle, thereby adversely affecting coating gas flow.     

Continued self-similar breakup of drops in viscous continuous phase in agitated vessels

Drop breakup in viscous liquids in agitated vessels occurs in elongational flow around impeller blade edges. The drop size distributions measured over extended periods for impellers of different sizes show that breakup process continues up to 15–20 h, before a steady state is reached. The size distributions evolve in a self-similar way till the steady state is reached. The scaled size distributions vary with impeller size and impeller speed, in contrast with the near universal scaling known for drop breakup in turbulent flows. The steady state size of the largest drop follows inverse scaling with impeller tip velocity. The breadth of the scaled size distributions also shows a monotonic relationship with impeller tip velocity only.     

Electrical behavior of silver particulate films deposited on 8 MeV electron beam irradiated softened polystyrene substrates

Results of the investigations carried out on the electrical behavior of silver particulate films deposited on electron beam irradiated polystyrene (PS) coated substrates held at a temperature of 455 K in a vacuum of 8 × 10⁻⁶ torr at a constant deposition rate of 0.4 nm/s are reported. It is known that when metals are evaporated on to softened polymer substrates, subsurface particulate structures are formed whose morphology is dependent on deposition parameters. Further, it was shown that the morphology is dependent on polymer-metal interaction. The present work demonstrates that the polymer-metal interaction can be brought about in inert polymers like PS by electron irradiation. The results indicate that the films deposited on PS irradiated to a dose of 20 and 25 kGy gives rise to smaller clusters with smaller inter-cluster separation, better suited for sensor applications. The induced polymer-metal interaction is attributed to the creation of free radicals due to the 8 MeV electron irradiation.     

Evaluation of the physical and mechanical properties of high drug load formulations: Wet granulation vs. novel foam granulation

The purpose of this study was to evaluate the influences of intrinsic drug mechanical properties and different granulation binder delivery processes on the physical and mechanical properties of high drug load granulations after wet granulation. Formulations (80% w/w) of acetaminophen (APAP), metformin and aspirin, which are brittle, viscoelastic, and ductile, respectively; were granulated by high-shear wet granulation. Two modes of binder delivery for wet granulation, either conventional or binder foam, were investigated. Particle size, surface area and pore size of the granulations were characterized. Compacts were prepared at a solid fraction of 0.9 under tri-axial decompression and Hiestand indices (worst-case bonding index (BI_w) and brittle fracture index (BFI)) of the compacts were determined. APAP formulations exhibited the smallest geometric mean particle sizes (d_g) and showed only slight differences in d_g values between the two granulation processes. Binder delivery mode affected mechanical properties of the granulated model drugs differently. Foam granulation appeared to enhance the granule plasticity for APAP while aspirin showed a mixed deformation mechanism based on both its high BI_w and high BFI values. The higher BI_w value for aspirin after foam granulation may be attributed to improved binder distribution among particles during granulation. On the other hand, conventional wet granulation improved the plasticity of metformin as measured by the higher BI_w and lower BFI values. Therefore, conventional wet granulation process conferred advantages in manufacturability and product quality for metformin; as compared to foam granulation which did not enhance plasticity for metformin. Based on this study, a wet granulation process can be selected based on knowledge of the intrinsic drug mechanical properties.