Rate Model and Mechanism of Liquid-Phase Oxidation of Propionaldehyde

A rate equation is developed for the liquid-phase oxidation of propionaldehyde with oxygen in the presence of manganese propionate catalyst in a sparged reactor. The equation takes into account diffusional limitations based on Brian's solution for mass transfer accompanied by a pseudo m-. nth-order reaction. Sauter-mean bubble diameter, gas holdup, interfacial area, and bubble rise velocity are measured, and rates of mass transfer within the gas phase and across the gas-liquid interface are computed. Statistically designed experiments show the adequacy of the equation. The oxidation reaction is zero order with respect to oxygen concentration, 3/2 order with respect to aldehyde concentration, and order with respect to catalyst concentration. The activation energy is 12.1 kcal/g mole.

A lifespan perspective on creativity and innovation at work

In this review, we address the relationship of aging with creativity and innovation at work. Organizing our review around the triad of person, environment, and behavior, we first discuss relevant theories and empirical findings from the creativity/innovation and aging literatures, and then review meta-analytical and primary studies on the aging-creativity/innovation relationship. In contrast to prevalent age stereotypes, we show that the empirical literature does not support direct, zero-order relationships, but that more complex (moderated, indirect, and curvilinear) relationships are highly plausible. We illustrate this point with a discussion of research on aging and scientific creativity. Finally, we outline opportunities for future research, both methodological and conceptual.

Modeling of heat and mass transfer for solid state fermentation process in tray bioreactor

A mathematical model is developed to simulate oxygen consumption, heat generation and cell growth in solid state fermentation (SSF). The fungal growth on the solid substrate particles results in the increase of the cell film thickness around the particles. The model incorporates this increase in the biofilm size which leads to decrease in the porosity of the substrate bed and diffusivity of oxygen in the bed. The model also takes into account the effect of steric hindrance limitations in SSF. The growth of cells around single particle and resulting expansion of biofilm around the particle is analyzed for simplified zero and first order oxygen consumption kinetics. Under conditions of zero order kinetics, the model predicts upper limit on cell density. The model simulations for packed bed of solid particles in tray bioreactor show distinct limitations on growth due to simultaneous heat and mass transport phenomena accompanying solid state fermentation process. The extent of limitation due to heat and/or mass transport phenomena is analyzed during different stages of fermentation. It is expected that the model will lead to better understanding of the transport processes in SSF, and therefore, will assist in optimal design of bioreactors for SSF.

Exact complex-wave reconstruction in digital holography

We address the problem of exact complex-wave reconstruction in digital holography. We show that, by confining the object-wave modulation to one quadrant of the frequency domain, and by maintaining a reference-wave intensity higher than that of the object, one can achieve exact complex-wave reconstruction in the absence of noise. A feature of the proposed technique is that the zero-order artifact, which is commonly encountered in hologram reconstruction, can be completely suppressed in the absence of noise. The technique is noniterative and nonlinear. We also establish a connection between the reconstruction technique and homomorphic signal processing, which enables an interpretation of the technique from the perspective of deconvolution. Another key contribution of this paper is a direct link between the reconstruction technique and the two-dimensional Hilbert transform formalism proposed by Hahn. We show that this connection leads to explicit Hilbert transform relations between the magnitude and phase of the complex wave encoded in the hologram. We also provide results on simulated as well as experimental data to validate the accuracy of the reconstruction technique. (C) 2011 Optical Society of America

Artifact-free reconstruction from off-axis digital holograms through nonlinear filtering

We present experimental investigation of a new reconstruction method for off-axis digital holographic microscopy (DHM). This method effectively suppresses the object auto-correlation, commonly called the zero-order term, from holographic measurements, thereby suppressing the artifacts generated by the intensities of the two beams employed for interference from complex wavefield reconstruction. The algorithm is based on non-linear filtering, and can be applied to standard DHM setups, with realistic recording conditions. We study the applicability of the technique under different experimental configurations, such as topographic images of microscopic specimens or speckle holograms.

Influence of HZSM-5 catalyst on the thermal degradation of poly(vinyl chloride) in solution

The kinetics of thermal degradation of poly(vinyl chloride) (PVC) in solution was investigated at various temperatures (210-250degreesC). The degradation rate coefficients were determined from the time evolution of the molecular weight distribution (MWD). The energy of activation, determined from the temperature dependence of the rate coefficient, was 26.6 kcal/mol. The degradation of PVC was also studied in the presence of a catalyst (HZSM-5 zeolite). The results indicated that increase of the degradation rate of PVC is first order with the HZSM-5 concentration up to 50 g/L and zero order at higher concentrations. The thermal degradation kinetics of PVC in the presence of 50 g/L of the catalyst was studied at various temperatures. The temperature dependency of the rate coefficient was used to calculate the activation energy (21.5 kcal/mol). This is consistent with the observation that the presence of a catalyst generally decreases the activation energy and promotes degradation. (C) 2002 John Wiley Sons, Inc.

Novel phenomenon of autoacceleration in the free radical oxidative polymerization of vinyl monomers: a thermochemical approach

A unique phenomenon of ‘autoacceleration’ was observed in a free radical polymerization of vinyl monomers and oxygen. Unlike the well known autoacceleration phenomenon in polymerization processes, this unusual phenomenon is not readily conceivable in terms of solution viscosity based reasoning. Surprisingly, we have observed manifestation of this new autoacceleration during free radical oxidative polymerization of some vinyl monomers at low conversions, where generally the polymerization reaction is zero order, the conversion–time plot are linear and viscosity effects are negligible. In the present paper, we interpret the mechanism of this new autoacceleration phenomenon on the basis of reactivity of the propagating radicals in terms of heat of formation data.

Differential Diffractive Reflectance Modulation Sensing

We fabricated a reflectance based sensor which relies on the diffraction pattern generated from a bio-microarray where an underlying thin film structure enhances the diffracted intensity from molecular layers. The zero order diffraction represents the background signal and the higher orders represent the phase difference between the array elements and the background. By taking the differential ratio of the first and zero order diffraction signals we get a quantitative measure of molecular binding while simultaneously rejecting common mode fluctuations. We improved the signal-to-noise ratio by an order of magnitude with this ratiometric approach compared to conventional single channel detection. In addition, we use a lithography based approach for fabricating microarrays which results in spot sizes as small as 5 micron diameter unlike the 100 micron spots from inkjet printing and is therefore capable of a high degree of multiplexing. We will describe the real-time measurement of adsorption of charged polymers and bulk refractometry using this technique. The lack of moving parts for point scanning of the microarray and the differential ratiometric measurements using diffracted orders from the same probe beam allows us to make real-time measurements in spite of noise arising from thermal or mechanical fluctuations in the fluid sample above the sensor surface. Further, the lack of moving parts leads to considerable simplification in the readout hardware permitting the use of this technique in compact point of care sensors.

Formulation development and evaluation of lamivudine controlled release tablets using cross-linked sago starch

Objectives: Modified starches based polymeric substances find utmost applicability in pharmaceutical formulation development. Cross-linked starches showed very promising results in drug delivery application. The present investigation concerns with the development of controlled release tablets of lamivudine using cross-linked sago starch. Methods: The cross-linked derivative was synthesized with phosphorous oxychloride and native sago starch in basic pH medium. The cross-linked sago starch was tested for acute toxicity and drug-excipient compatibility study. The formulated tablets were evaluated for various physical characteristics, in vitro dissolution release study and in vivo pharmacokinetic study in rabbit model. Results: In vitro release study showed that the optimized formulation exhibited highest correlation (R) in case of zero order kinetic model and the release mechanism followed a combination of diffusion and erosion process. There was a significant difference in the pharmacokinetic parameters (T-max, C-max, AUC, V-d, T-1/2, and MDT) of the optimized formulation as compared to the marketed conventional tablet Lamivir (R). Conclusion: The cross-linked starch showed promising results in terms of controlling the release behavior of the active drug from the matrix. The hydrophilic matrix synthesized by cross-linking could be used with a variety of active pharmaceutical ingredients for making their controlled/sustained release formulations.

Polyanhydrides of Castor Oil-Sebacic Acid for Controlled Release Applications

A family of high molecular weight castor oil (CO)-based biodegradable polyanhydrides was synthesized by a catalyst-free melt-condensation reaction between prepolymers of CO and sebacic acid (SA). The structure of the polymers was characterized by H-1 NMR and Fourier transform infrared spectroscopy, which indicated the formation of the anhydride bond along the polymer backbone. Thermal analysis and X-ray diffraction confirmed the semicrystalline nature of the polymers. Incorporation of SA enhanced the crystallinity of the polymer. The hydrophobic nature of these polymers was revealed by contact angle goniometry. Water wettability decreased with increase in SA content. Compressive tests demonstrated a sharp increase in strength and decrease in ductility with increasing SA content. In vitro hydrolytic degradation studies indicated surface-eroding behavior. The degradation rate decreased with an increase of SA content in the polymers because of increased crystallinity. The release studies of both hydrophobic and hydrophilic dyes followed zero-order kinetics. In vitro cell studies to assess the cytotoxicity of the polymer confirmed minimal toxicity of the degradation products. Thus, a family of CO-SA polyanhydrides have been synthesized and characterized for controlled release applications where the physical, mechanical, and degradation kinetics can be modulated by varying the weight fraction of the prepolymers.

Long-Term Sustained Release of Salicylic Acid from Cross-Linked Biodegradable Polyester Induces a Reduced Foreign Body Response in Mice

There has been a continuous surge toward developing new biopolymers that exhibit better in vivo biocompatibility properties in terms of demonstrating a reduced foreign body response (FBR). One approach to mitigate the undesired FBR is to develop an implant capable of releasing anti-inflammatory molecules in a sustained manner over a long time period. Implants causing inflammation are also more susceptible to infection. In this article, the in vivo biocompatibility of a novel, biodegradable salicylic acid releasing polyester (SAP) has been investigated by subcutaneous implantation in a mouse model. The tissue response to SAP was compared with that of a widely used biodegradable polymer, poly(lactic acid-co-glycolic acid) (PLGA), as a control over three time points: 2, 4, and 16 weeks postimplantation. A long-term in vitro study illustrates a continuous, linear (zero order) release of salicylic acid with a cumulative mass percent release rate of 7.34 x 10(-4) h(-1) over similar to 1.5-17 months. On the basis of physicochemical analysis, surface erosion for SAP and bulk erosion for PLGA have been confirmed as their dominant degradation modes in vivo. On the basis of the histomorphometrical analysis of inflammatory cell densities and collagen distribution as well as quantification of proinflammatory cytokine levels (TNF-alpha and IL-1 beta), a reduced foreign body response toward SAP with respect to that generated by PLGA has been unambiguously established. The favorable in vivo tissue response to SAP, as manifest from the uniform and well-vascularized encapsulation around the implant, is consistent with the decrease in inflammatory cell density and increase in angiogenesis with time. The above observations, together with the demonstration of long-term and sustained release of salicylic acid, establish the potential use of SAP for applications in improved matrices for tissue engineering and chronic wound healing.

Quasi-Dammann Grating With Proportional Intensity Array Spots

A quasi-Dammann grating is proposed to generate array spots with proportional-intensity orders in the far field. To describe the performance of the grating, the uniformities of the array spots are redefined. A two-dimensional even-sampling encode scheme is adopted to design the quasi-Dammann grating. Numerical solutions of the binary-phase quasi-Dammann grating with proportional-intensity orders are given. The experimental results with a third-order quasi-Dammann grating, which has an intensity proportion of 3:2:1 from zero order to second order, are presented. (C) 2008 Optical Society of America

Plane strain problem of growing crack for a perfectly plastic solid

In this paper, fundamental equations of the plane strain problem based on the 3-dimensional plastic flow theory are presented for a perfectly-plastic solid The complete governing equations for the growing crack problem are developed. The formulae for determining the velocity field are derived.The asymptotic equation consists of the premise equation and the zero-order governing equation. It is proved that the Prandtl centered-fan sector satisfies asymptotic equation but does not meet the needs of hlgher-order governing equations.

Static equilibrium of horizontal ring prominence

In 1980 the Beijing Observatory had successively observed sevesal rare completely closed ring prominences whose ring plane was approximately parallel to the solar surface with a characteristic life about 1—2 days. In this paper we discuss the static equilibrium of this kind of horizontal ring plasma under the simultaneous actions of magnetic force, gravity and pressure gradients. Assuming ring plasma with axisymmetry and rectangular plasma cross-section and adopting closed magnetic field boundary condition from the basic equations we obtain the exact zero order general solutions for magnetic field (force-free field) and density (pressure). We further obtain an eigen-solution for the zero order magnetic field and density as well as the first order magnetic field, thus giving a kind of the possible distribution of magnetic field and density for the horizontal closed ring prominence. The closed magnetic structure of ring prominence as presented in this paper, has no link with the force lines of the outside corona magnetic field. This is helpful to explain the great temperature difference between prominenee and corona.

Aplicação da calibração multivariada de ordem superior na resolução de espectros de fluorescência molecular para a quantificação de levofloxacino

Levofloxacino é uma fluorquinolona sintética de 3 geração. É eficaz contra uma variedade de infecções, incluindo o trato respiratório superior e inferior, trato urinário, obstétrico, ginecológico, e infecções dermatológicas. Com o objetivo de quantificar o levofloxacino em medicamentos e amostras de pacientes saudáveis e ter a resolução de seu espectro, foram realizados estudos preliminares em medicamento utilizando espectrofluorescência molecular com concentrações na faixa de 28,8 108 ng/mL e cromatografia líquida de alta eficiência (HPLC) na faixa de concentração de 2,9 10,8 g/mL; e também quantificação em urina de paciente em tratamento com o medicamento, usando os dois métodos citados. Após isso, foram feitos estudos conclusivos utilizando espectrofluorescência molecular e os métodos univariado e PLS para determinação de levofloxacino na faixa de concentração de 0 250 ng/mL e PARAFAC combinado com o método da adição de padrão, para quantificação de levofloxacino em urina de paciente saudável, na faixa de concentração de 0 150 ng/mL, com diluição da amostra em três níveis (100 x, 500 x e 1000x). O método de ordem zero se mostrou mais eficiente na determinação de levofloxacino em medicamento que o de primeira ordem, seus desvios padrão foram 2,0% e 7,9%, respectivamente. Já o PARAFAC com o método de adição de padrão apresentou melhores resultados com a urina, pois possibilitou a quantificação do antibiótico em uma amostra complexa, de forma mais precisa e exata com o aumento da diluição da urina, sem necessidade de tratamento prévio.