Enhanced visible-light photocatalytic oxidative desulfurization of model fuel over Pt-decorated carbon-doped TiO2 nanoparticles.

Modification of photocatalysts to improve their adsorption and photocatalytic activity in the oxidative desulfurization of liquid fuels has been reported by many investigators. In this study, Pt-decorated carbon-doped TiO2 nanoparticles were synthesized by hydrothermal and photo-deposition techniques and were subsequently used in photocatalytic oxidative desulfurization of dibenzothiophene (DBT) in n-heptane as a simulated liquid fuel with methanol as the extracting solvent. Carbon-doped TiO2 was first synthesized by a simple self-doping method. Pt was then loaded by a photo-deposition technique. The synthesized photocatalysts (labeled as YPt-CT where Y is percent Pt loading) were characterized by of X-ray diffraction (XRD), photoluminescence (PL), field emission scanning electron microscopy (FESEM), N2-physisorption, UV-Vis diffusive reflectance spectra (UV-Vis DRS), transmission electron microscopy (TEM), Fourier transform infrared spectra (FTIR), and nitrogen sorption measurements. The removal efficiency of DBT was 98% in the presence of 2 g/l of 0.5Pt-CT catalyst under visible-light irradiation (λ > 400 nm), ambient pressure, and reaction temperature of 40°C.

Equilibrium and Kinetic Insights into the Comprehensive Investigation of CO2, CH4, and N2 Adsorption on Cation-Exchanged X and Y Faujasite Zeolites.

The adsorption equilibria and kinetic performance of CO2, CH4, and N2 on pelletized cation-exchanged faujasite zeolites (with alkali, alkaline earth, and transition metal ions) have been investigated by an innovative volumetric apparatus simultaneously. The standard instrumental analytical techniques, including X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy (EDX), and atomic absorption spectroscopy (AAS), were utilized to characterize binder-free modified zeolites. EDX and AAS analyses revealed that the ion exchange was successfully achieved. The results indicate that the type of cation present in the zeolite framework and the Si/Al ratio can have a significant impact on the adsorption capacity and kinetic performance. The obtained isotherms were determined by three isotherm models, and the Langmuir-Freundlich (Sips) model was found to show the best agreement with the experimental isotherm data for all gases. The CO2 uptakes of KX, MgX, and CaX reached 4.13, 4.79, and 5.48 mmol/g, respectively. The effective binary and kinetic selectivities of CO2/CH4 and CO2/N2 were also calculated. Among all samples, KX showed the highest CO2/CH4 and CO2/N2 selectivities of 54.46 and 91.62, respectively. Pseudo-first-, pseudo-second-order, and Avrami kinetic models were fitted to the experimental kinetic data to analyze the adsorption kinetics. Finally, the macropore diffusion coefficient (Dp) and microporous diffusional time constant (Dc/rc2) were estimated by correlating the micropore-macropore kinetic model with the experimental fractional uptake curves. Among the ion-exchanged zeolite samples, the K+ form exhibits a suitable performance in terms of kinetic behavior and adsorption capacity.

Experimental study and kinetic modeling of methanol conversion to propylene with co-feeding of C4 and C5/C6 hydrocarbon cuts over a ZSM-5 catalyst.

Extensive experimental data were used to develop a comprehensive kinetic model for the methanol to propylene (MTP) process over a ZSM-5 catalyst. Preliminary experiments were performed to determine the reaction conditions that would ensure the absence of external (film) and internal mass transfer resistances. The kinetic experiments were subsequently carried out at 420-500 °C under conditions where mass transfer limitations were absent. A detailed reaction network was proposed for the MTP process based on the experimental product distribution and various reported kinetic models in the literature. According to the first series of experiments (without C4 and C5/C6 recycle streams) conducted at various temperatures, the best yield for propylene production was achieved at 480 °C with a water to methanol ratio of 0.7. Subsequently, kinetic experiments were performed at 480 °C and a water to methanol ratio of 0.7 using feeds with different amounts of C4 and C5/C6 hydrocarbons as recycle streams. Species material balances for the integral tubular reactor along with power-law rate functions and the Arrhenius equation for rate constants were employed in an optimization algorithm to obtain the kinetic parameters. The predictive ability of the model was checked against experimental data, and the kinetic parameters were validated by additional experiments.

Unraveling Cancer Metastatic Cascade Using Microfluidics-based Technologies.

Cancer has long been a leading cause of death. The primary tumor, however, is not the main cause of death in more than 90% of cases. It is the complex process of metastasis that makes cancer deadly. The invasion metastasis cascade is the multi-step biological process of cancer cell dissemination to distant organ sites and adaptation to the new microenvironment site. Unraveling the metastasis process can provide great insight into cancer death prevention or even treatment. Microfluidics is a promising platform, that provides a wide range of applications in metastasis-related investigations. Cell culture microfluidic technologies for in vitro modeling of cancer tissues with fluid flow and the presence of mechanical factors have led to the organ-on-a-chip platforms. Moreover, microfluidic systems have also been exploited for capturing and characterization of circulating tumor cells (CTCs) that provide crucial information on the metastatic behavior of a tumor. We present a comprehensive review of the recent developments in the application of microfluidics-based systems for analysis and understanding of the metastasis cascade from a wider perspective.

A catalyzed method to remove polychlorinated biphenyls from contaminated transformer oil.

The disposal of polychlorinated biphenyls (PCBs) as persistent organic pollutants from the environment has been normally performed by isolation from soil or water because of their biological activity and toxic potential. In the present investigation, catalytic hydrodehalogenation was used to detoxify PCBs-contaminated transformer oil. All reactions were directed on an oil containing 11.09 wt% of PCBs utilizing palladium supported on multi-walled carbon nanotubes (Pd/MWCNTs). The amount of hexa-chlorine homologues reduced considerably from 5.07% to less than 800 ppm utilizing HDC at the atmosphere of argon. Moreover, the amounts of long half-lives and bioaccumulative congener of PCB 153 decreased considerably from 3.2% to less than 200 ppm. Besides, the quantity of some environmental pollutants like PCB 105 as a mono-ortho-substituted congener decreased considerably. The significant effects of reaction time, reaction temperature, and catalyst concentration on the efficiency were confirmed and modeled through Box-Behnken design. The optimal reaction condition with an efficiency of 96.67% was 70°C, with catalyst loading of 8 wt% and reaction time of 3.23 h. Furthermore, the quantity of turnover frequency of Pd/MWCNTs showed that it has more activity than palladium-carbon active supported in the ambient pressure without utilizing hydrogen gas in transformer oil complex. The study of the kinetic model revealed that the required activation energy (of 12.99 kJ/mol) to remove PCBs from transformer oil utilizing the present catalyst was lower than other catalyzed hydrodechlorination methods.

A new insight to deformability correlation of circulating tumor cells with metastatic behavior by application of a new deformability-based microfluidic chip.

Isolation and characterization of circulating tumor cells (CTCs) found in blood samples of cancer patients have been considered as a reliable source for cancer prognosis and diagnosis. A new continuous microfluidic platform has been designed in this investigation for simultaneous capture and characterization of CTCs based on their deformability. The deformability-based chip (D-Chip) consists of two sections of separation and characterization where slanted weirs with a gap of 7 µm were considered. Although sometimes CTCs and leukocytes have the same size, the deformability differs in such a way that can be exploited for enrichment purposes. MCF7 and MDA-MB-231 cell lines were used for the initial evaluation of the D-Chip performance. In the separation section, cancer cells were isolated based on deformability differences with an efficiency of higher than 93% (∼average capturing capacity of 2085 out of 2200 cancer cells ml-1) and with significantly high purity (15-40 WBCs ml-1; ∼5 log depletion of WBCs). Cancer cells were categorized based on the deformability difference in the characterization section. Subsequently, 15 clinical blood samples from breast cancer patients were analyzed by the D-Chip. Suggest 'The chip detected CTCs in all patient samples, processed the blood sample at a high throughput of 5.3 ml/h, and properly categorized CTCs based on deformability differences. Further characterization showed that the highly deformable breast cancer CTCs in our patient samples also showed higher potential of metastasis in support of a broader correlation between deformability of CTCs and metastatic behavior.

Oxidation of toluene in humid air by metal oxides supported on γ-alumina.

Monometallic and bimetallic supported metal oxides catalysts on γ-alumina were prepared by heterogeneous deposition-precipitation. The γ-alumina used as a support was synthesized by the sol-gel and the co-precipitation methods. Supports and catalysts were characterized by Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The performance of the prepared catalysts was studied for total oxidation of toluene in air at different relative humidity and oxidation temperatures. Efficiency of bimetallic catalysts for deep oxidation of toluene was higher than copper oxide supported on γ-alumina. Although increasing the lanthanum, cobalt, and nickel loading on the support led to a modified catalyst surface and morphology, the catalytic activity of bimetallic catalysts decreased with increasing lanthanum, cobalt, and nickel content due to the reduced amount of copper oxide which has a higher activity for oxidation of volatile organic compounds. The γ-alumina prepared by the sol-gel method using ethanol as a solvent (AlSE) was the best support and La-Cu/AlSE had the best performance (toluene removal efficiency >90%). In addition, the presence of water vapor in the feed had a negative effect on toluene conversion.

Influence of external mass transfer limitation on apparent kinetic parameters of penicillin G acylase immobilized on nonporous ultrafine silica particles.

Immobilization of enzymes on nonporous supports provides a suitable model for investigating the effect of external mass transfer limitation on the reaction rate in the absence of internal diffusional resistance. In this study, deacylation of penicillin G was investigated using penicillin acylase immobilized on ultrafine silica particles. Kinetic studies were performed within the low-substrate-concentration region, where the external mass transfer limitation becomes significant. To predict the apparent kinetic parameters and the overall effectiveness factor, knowledge of the external mass transfer coefficient, k(L)a, is necessary. Although various correlations exist for estimation of k(L)a, in this study, an optimization scheme was utilized to obtain this coefficient. Using the optimum values of k(L)a, the initial reaction rates were predicted and found to be in good agreement with the experimental data.

Application of an optimization algorithm for estimating intrinsic kinetic parameters of immobilized enzymes.

A simple optimization methodology is applied to estimate the intrinsic kinetic parameters for both reversible and irreversible unireactant immobilized enzyme systems that follow the Michaelis-Menten mechanism. The method utilizes a direct-search optimization algorithm along with the numerical solution of the governing differential equations. The usefulness and validity of the method is demonstrated by comparing the predicted values of the intrinsic kinetic constants using the proposed method with a series of experimental values reported in the literature for different immobilized enzyme systems with irreversible and reversible reactions.